The problems of low polishing efficiency and serious surface damage in the processing of silicon carbide (SiC) ceramics are well-known. In view of the above problems, a new method of photocatalytic vibration composite polishing (PVCP) combined with a compound control strategy was proposed. A vibration-assisted device was developed, and a compound control system was designed for the device to improve the trajectory tracking accuracy. Experiments were carried out to verify the effectiveness of the vibration-assisted device and the compound control system. In addition, methyl orange degradation and fading experiments, redox potential measurement experiments, and SiC ceramic surface hardness characterization experiments were carried out to reveal the effects of vibration and photocatalytic parameters on polishing solution oxidation and SiC ceramic surface mechanical properties. Finally, the effects of photocatalysis, vibration frequency, amplitude, and the compound control system on the polishing effect were analyzed. The results show that when the UV intensity is 100%, the polishing force is 3-4N, the vibration frequency is 400 Hz, the amplitude is 15 μm, and the surface roughness of SiC ceramics is reduced by about 11 nm after the introduction of the compound control system, which verifies the effectiveness of the combination of the compound control system and PVCP.