Intermetallic compounds are increasingly being expected to be utilized in tribological environments, but to date their implementation is hindered by insufficient ductility at low and medium temperatures. This paper presents a novel multiphase intermetallic alloy with the chemical composition of Mo–40Ni–13Si (at %). Microstructure characterization reveals that a certain amount of ductile Mo phases formed during the solidification process of a ternary Mo–Ni–Si molten alloy, which is beneficial to the improvement of ductility of intermetallic alloys. Tribological properties of the designed alloy—including wear resistance, friction coefficient, and metallic tribological compatibility—were evaluated under dry sliding wear test conditions at room temperature. Results suggest that the multiphase alloy possesses an excellent tribological property, which is attributed to unique microstructural features and thereby a good combination in hardness and ductility. The corresponding wear mechanism is explained by observing the worn surface, subsurface, and wear debris of the alloy, which was found to be soft abrasive wear.