A novel approach of chemical mechanical polishing (CMP) is developed for mercury cadmium telluride (HgCdTe or MCT) semiconductors. Firstly, fixed-abrasive lapping is used to machine the MCT wafers, and the lapping solution is deionized water. Secondly, the MCT wafers are polished using the developed CMP slurry. The CMP slurry consists of mainly SiO2 nanospheres, H2O2, and malic and citric acids, which are different from previous CMP slurries, in which corrosive and toxic chemical reagents are usually employed. Finally, the polished MCT wafers are cleaned and dried by deionized water and compressed air, respectively. The novel approach of CMP is environment-friendly. Surface roughness Ra, and peak-to-valley (PV) values of 0.45, and 4.74 nm are achieved, respectively on MCT wafers after CMP. The first and second passivating processes are observed in electrochemical measurements on MCT wafers. The fundamental mechanisms of CMP are proposed according to the X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. Malic and citric acids dominate the first passivating process, and the CMP slurry governs the second process. Te(4+)3d peaks are absent after CMP induced by the developed CMP slurry, indicating the removing of oxidized films on MCT wafers, which is difficult to achieve using single H2O2 and malic and citric acids solutions.