Composites of polyphenylene sulfide reinforced with Kevlar 29 fiber were prepared by compression molding. The friction and wear behavior of the composites was examined with a pin-on-disc test rig. The morphologies and elemental composition of the transfer films on the counterface were analyzed with a scanning electron microscope equipped with an energy dispersive spectrometer. The tribochemical changes of polyphenylene sulfide composites during friction were examined by means of X-ray photoelectron spectroscopy. It has been found that the inclusion of Kevlar fiber increases the wear resistance of polyphenylene sulfide considerably. A discontinuous and thick transfer film forms on the counterface against unfilled polyphenylene sulfide, while a thin and uniform transfer film is generated on the counterface against the composite with 30% Kevlar fiber. The Kevlar fiber as a reinforcing agent promotes the decomposition and oxidation of the polymer matrix by way of increasing the frictional heating and the wear face temperature. This helps to increase the bonding strength of the transfer film on the counterface, and subsequently increases the wear resistance of the composites.