Ceria (CeO2)-based abrasives are widely utilized in ultra-precision grinding and chemical mechanical polishing (CMP) applications over silica materials due to their unique physicochemical properties. Both mechanical and chemical contributions to polishing processes are highly affected by the size, shape, structure, component, defect of CeO2 abrasives. Herein, the composites involved mesoporous silica (mSiO2) cores and La- or Yb-doped CeO2 shells were synthesized and characterized in terms of X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, scanning transmission electron microscopy–energy dispersive X-ray mapping methods. The polishing effectiveness of the proposed composites toward quartz glass was experimentally evaluated under both CMP and ultraviolet irradiation-assisted photochemical mechanical polishing (PCMP) conditions. The polishing results indicated that the low-modulus mSiO2 cores strongly exerted the cushion effects for the friction and abrasion to substrates. Consequently, the heterostructured mSiO2/La-CeO2 and mSiO2/Yb-CeO2 abrasive systems offered nearly non-damage and ultra-smooth surfaces with angstrom-level roughness compared to conventional rigid abrasives. The enriched Ce3+ and oxygen vacancy defects at La- and Yb- doped CeO2 surfaces were responsible for the improvements of tribochemical and photochemical activities, thus allowing evidently enhanced removal efficiency with the assistance of ultraviolet irradiation. A possible polishing mechanism on the multi-component abrasive systems was also proposed.