In this study, the effect of Carbon/PEEK composites on the tribological properties has been investigated. Also, its validity has been tested in the capacity of alternative materials of the Ti-based materials used for artificial hip joint. Moreover, this work evaluated the mechanical properties according to the fiber ply orientation, along with the fractured surfaces of the carbon/PEEK composites. The composites with a unidirectional orientation had higher tribological properties than those with a multidirectional orientation. This was caused by the debonding between the carbon fiber and the PEEK, which was proportional to the contact area between the sliding surface and the carbon fiber. The friction test results showed that there were no significant differences in relation to the fiber ply orientation. However, the friction properties of the carbon/PEEK composites were higher than those of the carbon/epoxy composites. In addition, the results showed that a composite that slid in a direction normal to the prepreg lay-up direction had a smaller friction coefficient than one that slid in a direction parallel to the prepreg lay-up direction.