4H silicon carbide (4H-SiC) wafers are widely used in high-power, high-temperature, and high-frequency electronics owing to their excellent physical and electrical properties. In the processing of 4H-SiC wafers, chemical-mechanical polishing (CMP) is commonly employed to realize atomic-scale smoothness, damage-free surface, and global planarization. The CMP process is the synergy of wet oxidation and mechanical grinding, whose efficiency significantly relies on the oxidation process. Therefore, understanding the wet oxidation mechanism of Si face and C face of 4H-SiC wafers is critical to high-efficiency double-side CMP. In this work, the anisotropic CMP performance of Si face and C face of 4H-SiC wafers are investigated. It has been found that the material removal rate of the C face is 2–3 times that of the Si face. The thicknesses of the transient oxide layer on the C face and Si face are 8.71 nm and 3.50 nm, respectively. X-ray photoelectron spectroscopy analysis reveals that the oxygen content on the C face is higher than that on the Si face after wet KMnO4 oxidation. This indicates that the C face of 4H-SiC is easier to oxidize, which results in more oxides that that on the Si face of 4H-SiC. Our work shows that accelerating the oxidation of the Si face of 4H-SiC wafers during the simultaneous double-sided CMP process is crucial for the efficient polishing of 4H-SiC wafers.