The wear and friction in the pitch region of the centre of polymer gear teeth are not well understood. The transition around this point of the tooth between rolling and sliding has an important effect on the durability of polymer gear drives and can be simulated using a twin-disc configuration. This paper investigates the rolling–sliding wear behaviour of two poly-ether-ether-ketone (PEEK) discs running against each other with a simplified method of analysing and understanding the dynamic response of high performance polymeric gear teeth. Tests were conducted without external lubrication over a range of loads and slip ratios, using a twin-disc test rig. The wear and friction mechanisms were closely related to surface morphology, with changes in crystallinity correlating with the severity of operating conditions. Observed failure mechanisms were also related to the structure of the contact surfaces, and included surface melting and contact fatigue. Overall the PEEK discs were capable of running at low slip ratios for both low and high loads. Their performance reduced with an increase of the slip ratio. The results presented can be used in conjunction with the design process to allow the PEEK to be engineered for a specific high performance gear contact conditions. The wear of poly-ether-ether-ketone in unlubricated rolling–sliding contact – simulation of high performance polymer gear applications Display omitted •Tribology of PEEK in dry, roll–slide conditions studied against load and slip-ratio.•Twin discs simulate extremes of polymer gear contact which are not well understood.•Wear, friction and temperature of PEEK discs increased with slip ratio and load.•Wear rates for PEEK were significantly lower than for other similarly tested polymers.•Results can be used to design more effective, highly loaded, and polymeric gear systems.