The material of the mating gear influences the fatigue life of polymer gears. The bending fatigue characteristics of polyamide 66 asymmetric gears (34°/20° and 20°/34°) corresponding to steel–polymer and polymer–polymer material combinations were investigated. The performance of symmetric gear pairs (20°/20°) was determined to serve as a comparison. Quasi-static numerical simulations were performed in a finite element analysis tool to predict root bending stress, load sharing ratio, and tooth deflection. The bending fatigue strength of steel–polymer and polymer–polymer pairs of each test configuration was determined using bending fatigue tests. The load sharing ratio and root bending stress of polymer–polymer pairs decreased substantially compared to steel–polymer pairs. The extent of deflection-induced load sharing was greater in polymer–polymer pairs. The bending fatigue life of polymer–polymer pairs was lower than that of steel–polymer pairs owing to the higher operating temperature. In polymer–polymer pairs, polymer driving and driven gears increased the heat generated and diminished the heat dissipation to the environment. In steel–polymer and polymer–polymer pairs, the configuration with the highest bending fatigue strength was 34°/20° and 20°/34°, respectively. This divergence was caused by the increase in temperature difference between the two configurations for polymer–polymer pairs. Analysis of hysteresis loops indicated that the loop area was higher for polymer–polymer pairs, signifying the increased amount of dissipated energy. No noticeable variation was observed between the failure modes of steel–polymer and polymer–polymer pairs despite the significant difference in the operating temperatures. The bending stress and operating temperature were the dominant factors affecting the performance of steel–polymer and polymer–polymer gear pairs, respectively.