This study was to correctly estimate the friction and wear behavior of carbon fiber and PEEK sheet composites, and the validity of using them as alternatives to the metal-based materials used for artificial hip joints. Moreover, this work evaluated the friction coefficient according to the fiber ply orientation, along with the fractured surfaces of the carbon/PEEK composites. The unidirectional composites had higher friction coefficients than those multidirectional composites. This was caused by the debonding between the carbon fiber and the PEEK sheet, which was proportional to the contact area between the sliding surface and the carbon fiber. The friction test results showed that there was no significant differences in relation to the fiber ply orientation. However, in a case where the speed was 2.5 m/s, the friction coefficient was relatively large for configuration I. The friction surface of the specimen was analyzed using an electron microscope. In all cases, the debonding of the fiber and PEEK could be confirmed.