In 1960, the RAF issued Specification 239 for a strategic transport, which resulted in an order being placed by the Air Ministry with Vickers in September 1961 for five VC10s. The order was increased by an additional six in August 1962, with a further three aircraft cancelled by BOAC added in July 1964. The military version (Type 1106) was a combination of the Standard combi airframe with the more powerful engines and fin fuel tank of the Super VC10. It also had a detachable in-flight refuelling nose probe and an auxilary power unit in the tailcone. Another difference from the civil specification was that all the passenger seats faced backwards for safety reasons.

The first RAF machine (designated VC10 C Mk. 1, often abbreviated to VC10 C1), was delivered for testing on 26 November 1965, with deliveries to No.10 Squadron beginning in December 1966 and ending in August 1968. The VC10s were named after Victoria Cross (VC) medal holders, displaying the VC holder's name above the forward passenger door. VC10 C1 aircraft were supplied to the RAF in specific configuration of a forward freight door (as per the K3), the "super" VC10 wing (as per the K3 and K4) and the fin fuel tank.

One aircraft (XR809) was leased to Rolls-Royce for flight testing of the RB211 turbofan between 1969 and 1975. On return to the RAF it was found that the airframe had become distorted, due to the increase in power from the RB211 fitted to one side of the fuselage over the Conways fitted to the other side. It considered uneconomical to repair and was instead used for SAS training, before being scrapped.

In late 1977, studies were started into converting redundant commercial VC10s into air-to-air refuelling tankers, with the RAF placing a contract with BAe to convert five former BOAC (that had been operated by Gulf Air) Standard VC10s and four former East African Airways Super VC10s as air-to-air refuelling tankers. These were designated VC10 K2 and VC10 K3 respectively. During conversion, extra fuel tanks were installed in what was previously the passenger cabin. These increased the theoretical maximum fuel load to 85 tons/77 tonnes (K2) and 90 tons/82 tonnes (K3); the fin fuel tank of the Super VC10 making the difference. In practice, the fuel load would be capped by the maximum take-off weight before the tanks are completely full. Both variants had refuelling pods mounted under the wings and a centreline refuelling point, known as a Hose Drum Unit (HDU), was installed in the rear freight bay. An in-flight refuelling probe was fitted on the nose, allowing fuel to be taken from the VC10, Victor or TriStar tankers.

Conversion to K2, K3 and K4 tanker role of the previous civil aircraft took place at BAe Systems Filton site. Because the K3s had a forward freight door this facilitated the insertion of five upper fuselage tanks in the main fuselage of the aircraft. In the case of the K2s, there was no forward freight door and it was required to dismantle a large section of the fuselage roof structure for the insertion of the five upper fuselage tanks. This proved to a mammoth task. In the K2 and K3 conversions extensive floor reinforcement was required to accommodate the additional weight of the five tanks and fuel load. K2 and K3 aircraft were classed as three point tankers, consisting of two wing mounted HDU and one centre fuselage HDU.

In 1981, 14 former British Airways Super VC10s were purchased, and these were placed in storage and some were used for spare parts. The Dual Carousel navigation system of the Supers were fitted to the Operation Black Buck Vulcan bombers during the Falklands War to enable them to navigate over open ocean. In the early 1990s, five of the aircraft were revived and converted to VC10 K4 tankers. Upon examination prior to the first "major" in-depth servicing of the K4s it was discovered that there was extensive wing plank corrision in the lower surface of the wings. This was attributed mainly to the storage method used prior to conversion, whereby the wing tanks were defuelled but then filled with water, in order to add ballast to the aircraft during storage. This led to an extensive wing plank corrosion rectification and in some cases plank replacement during subsequent major services. For the K4 conversions, as with the K2 aircraft, there was no facility of a forward freight door. For this reason it was decided that there would be no internal refuelling tanks fitted to the K4s. The K4 has identical refuelling equipment to the K2 and K3, but does not have any extra fuel tanks in the fuselage. Its fuel capacity remains at 80 tons (70 tonnes), the same as a Super VC10.

During the late 1980s and early 1990s, the 13 surviving C1s were also equipped with wing-mounted refuelling pods (HDUs) and re-designated as VC10 C1K dual-rôle two-point tanker/transports. Again, no extra tanks were provided and the fuel load remains at 80 tons (70 tonnes). The C1s did not therefore require the strengthened flooring. The conversions were undertaken by FR Aviation Limited based at Hurn Airport, near Bournemouth. The in-flight refuelling probe was a feature of the original RAF aircraft, but it was removed for a period during the 1970s and 1980s due to lack of use. The probe was refitted sometime before the tanker conversions took place.

In 1982 VC10 C1s were part of the airbridge between RAF Brize Norton and Wideawake Airfield on Ascension Island during Opertion Corporate, the campaign to retake the Falkland Islands. In 1991 9 K2s and K3s deployed to Bahrain, Saudi Arabia and Oman as part of Operation Granby, the UK's contribution to the campaign to remove Iraqi forces from Kuwait, during which they flew 381 sorties.

In 1992, XR806 suffered a flash fire in a wing fuel tank, whilst undergoing major maintenance and fuel leak rectification. The aircraft was repaired and returned to service. In 1997, XR806 was damaged beyond economic repair in a ground de-fuelling accident at RAF Brize Norton. The aircraft overbalanced backwards damaging the rear cone of the fuselage including the rear pressure bulkhead and lower sections of the rudder.

VC10s allowed RAF Bruggen-based Tornado GR1s to strike Serbian targets during Operation Allied Force in 1999.

Oman-based VC10s refuelled USAF and Marine Corps aircraft over Afghanistan as part of Opertion Veritas. Nine VC10s participated in Operation Telic, the UK's contribution to Opertion Iraqi Freedom.

The K2s were retired and scrapped between 2000 and 2003. In 2006 two VC10s were dispatched to Okinawa, Japan to undertake a lesser known role of the type; to collect nuclear debris tests using sampling pods replacing the refuelling pods. This was prompted by the North Korean Nuclear test.

VC10 air-to-air refuelling aircraft supported the British Air strikes on Libya on 19–20 March 2011 as part of the coalition operations to enforce UN Resolution 1973.

The surviving C1Ks and K3s serve as tanker/transports with No.101 Squadron at Brize Norton, Oxfordshire and the one remaining K4 supports No.1312 Flight at RAF Mount Plessant in the Falklands Islands. The VC10 and Lockeed TriStar tanker/transports are due to be replaced in RAF service by the Airbus A330 MRTT Voyager under the Future Strategic Tanker Aircraft Project. As of July 2012 they are expected to retire by 31 March 2013.

All servicing of the RAF fleet of VC10s was undertaken at RAF Brize Norton in a purpose built hangar. Known as "Base Hangar" when built in 1969 was considered the largest cantilever-roofed structure in Europe; a quarter of a mile in length with no internal supports. Six VC10 aircraft could be positioned inside with provide working space around the aircraft.

During the late 1980s, it was considered to move major servicing to RAF Abingdon near to RAF Brize Norton. Abingdon was closed and a new facility was built at RAF St.Athan, in South Wales - "1 Air Maintenance Sqn" (1 AMS). The first aircraft to undergo major servicing at the new facility entered in January 1993. One of the two lines was later turned over for the use of Tornado aircraft.

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