PA66 is a commonly used material for plastic gears due to its excellent high-temperature resistance, high strength, self-lubrication, and friction resistance. In this study, the effect of different humidity levels on the tribological properties of PA66 materials in self-mated contacts are investigated using a pin-on-disk test rig. The results show that the friction coefficient and wear rate of the PA66-PA66 sliding combination increase drastically after humidity treatment mainly due to the surface plasticization caused by water absorption and the decrease of cohesive strength and glass transition temperature. Moreover, the limiting PV value of PA66 materials decreased significantly after moisture absorption, and when the actual PV value exceeds this reduced material limit, the degree of friction and wear increases drastically. The wear mechanism of the PA66-PA66 sliding combination is mainly adhesive wear without humidity treatment. The wear mechanism is adhesive wear combined with abrasive wear after humidity treatment (50%, 70%, 90%, immersion in water) and abrasive wear is most significant at 50% humidity. Abrasive wear decreases with the increase of the moisture content, while adhesive wear increases.