Mo₂N films were synthesized using the reactive magnetron sputtering system in a mixture of argon and nitrogen, and the tribological properties were investigated at different testing temperatures against an Al₂O₃ counterpart. The relative intensity ratio (RIR) method was used to calculate the weight fraction of the tribo-film (MoO₃) on the wear tracks of the films. The results showed that the average friction coefficient first increased from 0.30 at 25 °C to 0.53 at 200 °C, and then decreased to 0.29 at 550 °C, while the wear rate decreased from 2.1 × 10⁻⁶ mm³/Nmm at 25 °C to 5.3 × 10⁻⁷ mm³/Nmm at 200 °C and then increased to 3.1 × 10⁻⁵ mm³/Nmm at 550 °C. The weight fraction of tribo-film was mainly attributed to changes in the average friction coefficient and the wear rate. Besides this, the relative humidity also influenced the tribological properties at 25–200 °C.