A Cr-free Ni-based self-lubricating composites with MoS₂ and Ag as lubricants were fabricated by the powder metallurgy method. The microstructures were examined. The mechanical properties and tribological behaviors of the composites were evaluated from room temperature to 800 °C. The fractography was observed and the fracture mechanisms were analyzed. The morphologies and the phase compositions of worn surfaces were determined and the wear mechanisms were elaborated. The results indicate that MoS₂ did not completely decompose after sintering, and the NiMoAl-MoS₂-Ag composite has the best tribological properties (0.22, 1.68 × 10⁻⁵) at 800 °C. The main wear mechanisms are micro-ploughing and plastic deformation. The improvement of tribological properties was attributed to the formation of the lubricating film consisting of NiO, Mo oxides, various molybdates, and Ag particles. The reactions resulting in these compositions are proposed. The mechanical properties degrade with the rise of temperature and the addition of lubricants. Both NiMoAl and NiMoAlAg alloys exhibit micro-void accumulation fracture while the composites with MoS₂ reveal intergranular fracture.