Chemical mechanical polishing (CMP) removal mechanisms of on-axis Si-face SiC wafer have been investigated through X-ray photoelectron spectroscopy (XPS), UV–visible (UV–vis) spectroscopy and atomic force microscopy (AFM). XPS results indicate that silicon oxide is formed on Si-face surface polished by the slurry including oxidant H2O2, but not that after immersing in H2O2 solution. UV–vis spectroscopy curves prove that •OH hydroxyl radical could be generated only under CMP polishing by the slurry including H2O2 and abrasive, so as to promote oxidation of Si-face to realize the effective removal; meanwhile, alkali KOH during CMP could induce the production of more radicals to improve the removal. On the other side, ultra-smooth polished surface with atomic step structure morphology and extremely low Ra of about 0.06 nm (through AFM) is obtained using the developed slurry with silica nanoparticle abrasive. Through investigating the variations of the atomic step morphology on the surface polished by different slurries, it's reveals that CMP removal mechanism involves a simultaneous process of surface chemical reaction and nanoparticle atomic scale abrasion.