The surface of metal mirrors is often polished by electroless coating with a Ni–P modified layer after single-point diamond turning. In practice, however, improvements in mirror quality are closely related to the polishing environment, polishing medium, and polishing force. If not adequately controlled, processing defects such as visible scratches can lead to the deterioration of surface roughness. Based on the Ni–P modified surface of a metal reflector mirror, this study optimizes the configuration of magnetorheological figuring (MRF) fluid and polishing process parameters so that MRF high-efficiency surface modification can be realized and the scratch problem can be resolved. The processing method of a high-performance metal mirror is developed by studying the high-efficiency and high-precision processing technology based on small head smoothing. The surface roughness achieved by the proposed method was better than Ra = 0.39 nm. The ultrasonic cleaning process effectively improved the surface roughness after processing. According to the combined processing technology developed in this study, the modified layer of the parabolic mirror with a diameter of 370 mm was processed, and the surface quality was increased from RMS = 338.684 nm to RMS = 21.267 nm.