Micro-electro-mechanical systems (MEMS) hemispherical resonant gyroscopes are used in a wide range of applications in defense technology, electronics, aerospace, etc. The surface roughness of the silicon micro-hemisphere concave molds (CMs) inside the MEMS hemispherical resonant gyroscope is the main factor affecting the performance of the gyroscope. Therefore, a new method for reducing the surface roughness of the micro-CM needs to be developed. Micro-ultrasonic machining (MUM) has proven to be an excellent method for machining micro-CMs; shear thickening fluids (STFs) have also been used in the ultra-precision polishing field due to their perfect processing performance. Ultimately, an STF-MUM polishing method that combines STF with MUM is proposed to improve the surface roughness of the micro-CM. In order to achieve the excellent processing performance of the new technology, a Categorical Boosting (CatBoost)-genetic algorithm (GA) optimization model was developed to optimize the processing parameters. The results of optimizing the processing parameters via the CatBoost-GA model were verified by five groups of independent repeated experiments. The maximum absolute error of CatBoost-GA is 7.21%, the average absolute error is 4.69%, and the minimum surface roughness is reduced by 28.72% compared to the minimum value of the experimental results without optimization.