To systematically investigate the influence of Si content and alloying elements on the tribological properties of AlSi alloys, samples with varying Si contents (6, 8, 10, 12 wt.%) and the Al10Si alloys modified with 2 wt.% Cr, 2 wt.% Mo, 2 wt.% Cr + 2 wt.% Mo, and 1 wt.% Ce were prepared via vacuum casting. The microstructures, mechanical properties, and tribological behaviors of these alloys were characterized using SEM, EDS, XRD, Vickers hardness and tribological testings. The results indicate that increasing the Si content leads to a gradual rise in hardness and a concurrent reduction in the friction coefficient. Al12Si exhibited a 19.7% increase in hardness and a 26.8% reduction in friction coefficient compared to Al6Si. The addition of alloying elements further enhanced these properties. Al10Si2Cr2Mo showed the highest hardness, attributable to the combined effects of solid-solution strengthening by Cr and Mo atoms in the α-Al matrix and dispersion strengthening from Al13Cr4Si4 and Mo3Si precipitates. Al10Si1Ce ranked second in hardness, due to grain refinement through Ce’s inhibition of grain growth. Al10Si2Cr2Mo also exhibited the best wear resistance, followed by Al10Si1Ce. The improvement is ascribed to microstructural refinement and the presence of dispersed hard phases (Al13Cr4Si4 and Mo3Si flakes, as well as fibrous Al2Si2Ce compounds), which suppress subsurface crack propagation and facilitate the formation of a continuous and dense mechanically mixed layer.