Polyetheretherketone (PEEK) is a designation given to materials of the polyaryletherketone family having a characteristic distribution of ether and ketone groups in the polymer backbone. PEEK materials have high strength and chemical resistance as well as very high melting points and glass transition temperatures. Because of this combination of properties, PEEK materials find use for wear application in extreme environments where they provide a light-weight and corrosion resistant bearing material that often does not require lubrication. An initial study focused on determining the effects of supplier and molecular weight on the wear of particular PEEK materials, in addition to the effect of contact pressure. This work is significant because it highlights the fact that tribologically relevant polymers, such as PEEK materials, vary greatly in terms of their polymer morphology and processing history, and this variation must be recognized by investigators when reporting wear data. Because of their light weight, chemical resistance, and self-lubricating properties, polymers are used in applications ranging from biomedical to aerospace. Some polymers exhibit significant differences in wear resistance based on whether they are in unidirectional or multidirectional sliding. Shear induced polymer chain orientation is believed to be responsible for this behavior. Polyetheretherketone (PEEK) has excellent wear resistance, but its multidirectional sliding behavior has not been thoroughly investigated. A factorial multidirectional pin-on-plate wear study of PEEK was conducted with a focus on molecular weight and sliding path directionality. These factors were studied for their correlation to overall wear performance. Additionally, transfer film thickness was measured at locations along the wear path using white light interferometry. A result of this work has been a greater understanding of PEEK wear mechanisms in various sliding configurations and how they relate to transfer film formation. A major outcome was the development of a quantitative metric to describe transfer film thickness and continuity. It was found that thinner more continuous transfer films form under sliding conditions that change direction rather than overlapping along the same path. The thinner more continuous transfer film was found to also correspond with statistically lower wear behavior. Scanning electron microscope (SEM) investigation of the transfer film and pin wear surface confirmed the relationship between transfer film quality and wear.