In this study, novel slags with a high basicity index were used to refine silicon melts with carbon dioxide injection to effectively remove Ti from metallurgical-grade silicon. Different compositions of the initial slag were used, and silicon samples were obtained during the refining. The results indicate that the Ti-removal rate initially increased with an increase in the basicity index, and it decreased after the basicity index exceeded 1.4. During the refining, silicon emulsification was observed at the slag–silicon interface, which was restricted by the increased basicity index of slags. Impurities that were concentrated in silicon droplets near the slag–silicon interfaces were oxidized, wetted by slags, and transferred to the slag phase. After 15 min of refining, up to 59 wt% of Ti in silicon could be removed and the Ti-concentrating phase in the slag contained 2.05 wt% of Ti. The results of this study provide a reference for low-cost Ti removal from metallurgical-grade silicon using a refining method.