The solid lubricant MoS₂ demonstrates excellent lubricating properties, but it spontaneously oxidizes and absorbs moisture in air, and thus results in poor wear resistance and short wear-life. In this study, the additive g-C₃N₄ (CN) was successfully combined with MoS₂ via hydrothermal synthesis as a solid lubricant for the first time. Meanwhile, a low friction coefficient (COF, μ = 0.031) and ultra-long wear-life of CN/MoS₂ compared to pure MoS₂ in air were demonstrated. The functional groups and good crystallinity of the lubricant material were characterized via Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD). The formed valence states in CN/MoS₂ were analyzed via X-ray photoelectron spectroscopy (XPS). The characterized results of the scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM) show the morphology and interior crystal phase structure of CN/MoS₂. From the cross-section analysis, the presence of iron oxide nanoparticles lubricating film is synergistic with CN/MoS₂ film during the friction process, resulting in its ultra-long wear-life. In particular, the friction mechanism of interlayer sliding friction combined with energy storage friction was analyzed and proposed.