Single-crystal sapphire (α-Al2O3) has been widely used in semiconductor, optics, communication, national defense, and other fields. Before application, an ultra-smooth surface which is scratch free and subsurface damage free is essential. Furthermore, the sapphire has unique qualities such as significant rigidity and chemical stability, which make it extremely arduous to process. Chemical mechanical polishing (CMP) is recognized as the final process to reduce the roughness and eliminate surface defects of a sapphire surface. In this review, the materials and equipment used for the chemical polishing of a sapphire wafer are summarized, and the surface nanoscale changes of sapphire wafer are reviewed from the angles of regulating polishing-process parameters, composition of polishing slurry including that which is nano-abrasive, a pH regulator, a complexing agent, and other additives, as well as hybrid CMP technologies. The outlook and future applications are also summarized.