The role of water in the tribochemical mechanisms of ultralow wear polytetrafluoroethylene (PTFE) composites was investigated by studying 10 and 20 wt % polyether ether ketone (PEEK)-filled and 5 wt % αAl2O3-filled PTFE composites. These composites were run against stainless-steel substrates in humidity, water, and dry nitrogen environments. The results showed that the wear behavior of both composites was significantly affected by the sliding environment. Both composites achieved remarkably low wear rates in humidity because of tribochemically generated carboxylate end groups that anchored the polymer transfer films to the steel substrate. In nitrogen, PTFE–PEEK outperformed PTFE−αAl2O3 because of polar carbonyl groups on PEEK, which increased the surface energy of PEEK, aiding it in adhering to the substrate and resulting in a transfer film. Both composites in water exhibited high wear. The water oversaturated the functional groups at the end of the polymer chains and prevented the formation of a transfer film.