Solid lubricating films have great advantages in extreme operating conditions. In this research, silver (Ag) was doped into the ZrMoN composite film to develop a composite polyphase structure with enhanced mechanical and tribological properties. A series of ZrMoN–Ag composite films with different Ag content were prepared. The results show that the composition phases of the composite films are fcc-Mo2N、fcc-ZrN, and nano-crystalline fcc-Ag was dispersed in the films. The ZrMoN–Ag composite films exhibited excellent mechanical properties with a hardness of 27.6 GPa and elastic modulus of 286.8 GPa. In addition, the ZrMoN–Ag composite film with Ag content of 11.88 at.% possessed the advantage of low friction coefficient in a wide temperature range, attributing mainly to the synergetic effect of Ag phase and friction oxidation products. This work provides a promising solution for designing solid self-lubrication composite in wide temperature domain.