Ceria (CeO2) particles are prevalent polishing abrasive materials. Trivalent lanthanide ions are the popular category of dopants for enriched surface defects and thus improved physicochemical properties, since they are highly compatible with CeO2 lattices. Herein, a series of dendritic-like mesoporous silica (D-mSiO2)-supported samarium (Sm)-doped CeO2 nanocrystals were synthesized via a facile chemical precipitation method. The relation of the structural characteristics and chemical mechanical polishing (CMP) performances were investigated to explore the effect of Sm-doping amounts on the D-mSiO2/SmxCe1−xO2−δ (x = 0–1) composite abrasives. The involved low-modulus D-mSiO2 cores aimed to eliminate surface scratch and damage, resulting from the optimized contact behavior between abrasives and surfaces. The trivalent cerium (Ce3+) and oxygen vacancy (VO) at CeO2 surfaces were expected to be reactive sites for the material removal process over SiO2 films. The optimal oxide-CMP performances in terms of removal efficiency and surface quality were achieved by the 40% Sm-doped composite abrasives. It might be attributed to the high Ce3+ and VO concentrations and the enhancement of tribochemical reactivity between CeO2SiO2 interfaces. Furthermore, the relationship between the surface chemistry, polishing performance as well as the actual role in oxide-CMP of the D-mSiO2/SmxCe1−xO2−δ abrasives were also discussed.