The effect of rare earth Ce on microstructure and friction and wear properties of HMn64-8-5-1.5 alloy was systematically studied. The results indicate that rare earth Ce plays the role of deoxidation, desulfurization, dehydrogenation and impurity removal during the smelting process, which can purify the alloy matrix and make the grain size remarkably refined. The friction and wear experiments show that the rare earth Ce can significantly improve the friction and wear properties of the material. When 0.2wt% Ce is added, the weight loss of the alloy is less than 25%. The wear mechanism of the alloy is analyzed by combining two kinds of friction and wear models. The major wear behavior of the alloy changes from adhesive wear to abrasive wear by adding 0.2 wt% Ce. The main reason for the change of wear mechanism of the alloy with and without the Ce addition is the effects of removing impurities and refining crystal grains by Ce, which increases the surface strength and ultimate deformation value of the alloy itself.