The Tomcat has an internal 6-barrel M61A1 Vulcan 20-mm Gatling-type gun located on the lower left side of the aircraft, underneath the pilot. It can carry AIM-7 Sparrows, AIM-9 Sidewinders, AIM-120 AMRAAMs, AIM-54 Phoenix missiles and up to 20 MK82 bombs (Mark Bombs). The heart and deadly aspect of the F-14 Tomcat is its unique ability to carry the Phoenix. The F-14 Tomcat was built for that purpose, and it is the only platform that can carry the Phoenix. At most, the F-14 Tomcat can carry up to 6 Phoenix which are been carried on 4 fuselage stations between the engines and on 2 pylons fitted on the fixed portion of the wing; 2 Sidewinders can be carried on the wing pylons above the Phoenix mount.

The first active-radar missile, the Phoenix was designed to shoot down Tu-22 bombers and their missiles. It is the biggest of all U.S. air-to-air missiles, and it is only carried on the F-14 Tomcat. Maximum range is more than 80 miles under ideal circumstances. A planned replacement for the Phoenix was cancelled in 1991. However, the expensive nature of the Phoenix missile (approx. U.S. 1 million) deems this missile as a last resort or for use against enemy Exocet or anti-ship missiles.

On 4 January 1989, 2 F-14s of VF-32 from the carrier USS JOHN F. KENNEDY (CV 67), then off the island of Crete in the Mediterranean, intercepted 2 Libyan MiG-23 Flogger-E aircraft and downed them both, 1 with a radar-guided Sparrow AAM and the other with an IR-seeking Sidewinder. The US pilots claimed to have seen 2 parachutes.

The Tomcats took part in Operation Desert Storm providing CAP (Combat Air Patrol) for bombers and other aircrafts as well as performing TARPS (Tactical Air Reconnaissance Pod System) missions. 100 F-14s flew 3,401 sorties as Combat Air Patrol (CAP) aircraft from 5 carriers during the air assault on Iraqi targets that began Operation Desert Storm; another 781 sorties were devoted to TARPS. One F-14 was gunned down by ground fire, but no other F-14 was lost. Only one combat kill was credited to a Tomcat using the AIM-9 Sidewinder air-to-air missile to target down an Iraqi Mi-8 "Hip", a Soviet-made transport helicopter. The rapid dismemberment of the Iraqi air defense system by coalition air attacks grounded virtually all Iraqi aircraft, leaving the F-14s with few aerial targets.

In late 1995, the F-14 Tomcat took on a new, and completely different role in military combat over targets in Bosnia...they became bombers. Dubbed "Bombcat's", these new bombers dropped LGB "smart bombs" while other aircraft painted the targets with lasers. Aircraft of VF-32 took part in Operation Desert Fox.