A series of experiments has been conducted to investigate the tribological properties of a TiN film sliding against GCr15 steel balls in ambient air, low vacuum and high vacuum environments. Various friction loads and sliding velocities were also applied. The TiN film displays a steady-state friction stage after the running-in stage in all the above environments, while the durations of running-in stages are different. The steady-state friction coefficients of the TiN film were around 0.56 in ambient air and 0.3 in the high vacuum environment (1 × 10⁻⁵ mbar). In the low vacuum (1 × 10⁻² mbar) environment, a low friction coefficient (around 0.19) was attained for all the friction tests on TiN film, irrespective of the applied load and sliding velocity. In the meantime, it was noticed that the applied loads and the sliding velocities would change the duration of the running-in stage before reaching the low friction coefficient. It is revealed by the analysis of wear tracks that the metal oxides induced by the tribo-chemical effect at the friction interface play an important role in affecting the tribological behaviors of the TiN films in different environments. The Raman results show that the main component of the metal oxides is hematite (α-Fe₂O₃), and the amount of iron oxide is related to the friction environment. The composition and quantity of iron oxides produced by the interfacial tribo-chemical effect affect the tribological behavior. The results also show that the mechanical wear process at the friction interface displays a polishing effect, which would reduce the surface roughness. The mechanical wear performance varies under different loads and velocities. The tribological tests results indicate that the interfacial tribo-chemical effect and mechanical wear process should be considered together rather than individually to interpret the tribological behaviors of TiN films in different environments.