Single-crystal silicon carbide (SiC) has poor machinability because of its low fracture toughness, and surface modification has become the first choice for SiC polishing to obtain a high removal rate and a smooth surface. However, the removal mechanism of SiC after modification remains unclear. In this study, diamond scratching experiments were performed on 4H–SiC after oxidation under two conditions. To reveal the material removal mechanism, the scratch morphology and subsurface defects were analysed using Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. The results showed that oxidation improved the scratch depth and critical depth for ductile removal, resulting in a smooth scratch surface with low damage. However, weak oxidation increased the median crack length and exacerbated the subsurface damage. The SiOxCy, C = O, C–O–C, and Si–O–Si functional groups produced during oxidation reduced the hardness and improved the machinability of the 4H–SiC substrate. On the other hand, strong oxidation reduced the generation of surface cracks, tearing, and spalling, and weakened the propagation of subsurface median cracks. These results prove that ultrasonic-assisted photocatalytic oxidation provides high removal efficiency and defect control, providing a new approach for the synergistic polishing of SiC substrates.