To reuse roller waste as a raw material of high performance green ceramic balls, three kinds of white alumina ceramic balls whose wear resistance were 2-3 times of the best high alumina ceramic ball with 90% Al2O3 were prepared, and the Al2O3 content of the prepared balls was 75%. It is found that the effect of calcia and magnesia on the wear resistance of ceramic balls is contrast to the accepted one: the wear rate of the ceramic balls prepared in CaO-Al2O3-SiO2 system is the lowest and the wear rate of the ceramic balls prepared in MgO-Al2O3-SiO2 is the highest. The main crystal phase of the ceramic ball is mullite and corundum. The ceramic ball granular is uniform and fine with 4-5 μm average size. The pore diameter is about 2 μm. The wear way of the ceramic balls is mainly transcrystalline fracture.