The tribological properties of a chemically complex intermetallic alloy (CCIMA) were enhanced through plasma nitriding surface treatment. The results revealed that nitriding led to the formation of complex nitrides, including TiN, AlN, BN, and CrN, on the alloy surface. Benefiting from this, the wear resistance of CCIMA has been significantly improved. At room temperature, plasma nitriding significantly reduced fatigue damage and oxidative wear, resulting in the wear rate of nitrided CCIMA (1.05 ± 0.36 × 10 -5 mm 3/Nm) being only one-fourteenth that of the un-nitrided substrate (1.49 ± 0.06 × 10 -4 mm 3/Nm). In addition, although the degree of delamination wear was exacerbated at elevated temperatures, the formation of the protective glaze layers allowed the nitrided CCIMA to maintain better wear resistance at 500 °C and 600 °C, with the wear rate of only 2.28 ± 0.49 × 10 -5 mm 3/Nm, and 5.38 ± 0.78 × 10 -5 mm 3/Nm, respectively. These findings provide an important theoretical and experimental basis for designing and developing new alloys with enhanced high-temperature wear resistance.