The abrasive is one of the important influencing factors during the chemical mechanical polishing (CMP) process. Although α-alumina is one of the most commonly used sapphire polishing abrasives due to its high hardness, it often results in surface damage. To receive lower surface roughness and high material removal rate, a common approach is to modify the surface of alumina. In this work, a series of alumina/metatitanic acid composite abrasives with core–shell structure were synthesized. The CMP performances of the pure alumina and alumina/metatitanic acid core–shell abrasives on sapphire substrates were investigated after polishing under the same conditions. Experimental results indicate that the alumina/metatitanic acid core–shell abrasives can not only improve the surface quality, but also further enhance the material removal rate. Furthermore, through the X-ray photoelectron spectroscopy test, this study investigated the chemical effect mechanism of the alumina/metatitanic acid core–shell abrasives in sapphire CMP. The results show that solid-state chemical reactions occur between metatitanic acid shell and sapphire surface during CMP process. We also investigated the mechanical friction mechanism through abrasive wear and adhesive wear.