According to the comparative experiments on friction and wear of Al–TiC, Al–Bi (RC) and Al–Bi–TiC alloys, the friction-reduction and wear-resistance mechanisms of TiC/Bi were systematically investigated. The alloys were examined via the scanning electron microscope equipped with an energy dispersive spectrometer and a shape-measuring laser microscope (VK-X100). Basing the achievements, the Bi-phase accumulates on the friction surface with gradual enrichment, possessing anti-friction and self-lubrication on the friction surface. The stable TiC/Bi self-lubricating layer of Al–Bi–TiC alloy make the values of the wear measurements reduce from 82.2 mg to 26.7 mg in 2 h. Meanwhile, TiC particles have uniform load capacity and interfacial pinning properties, which solve the peeling off from the worn surface of Bi-phase.