Photochemical mechanical polishing (PCMP) technique, involved the cooperation of light-driven surface modification and force-induced material removal, is expected to be a clean, high-quality, and high-efficiency processing method. Herein, mSiO2@CdS@CeO2 hybrids with mesoporous cores and double-layered core–shell heterostructures were constructed through a three-step strategy and utilized as novel abrasive systems towards PCMP applications. Morphological, structural, and optical characterizations were systematically performed to investigate the correlation between components and polishing performances of the proposed abrasive systems. The created CdS–CeO2 heterojunction contributed to the efficient separation of photogenerated charge carriers and the production of highly reactive oxygen species, thus promoting the formation of photochemically reacted layers. The tribochemical activity and material removal enhancements might be attributed to the enrichments of trivalent cerium and oxygen vacancy in CeO2 layer after introducing CdS intermediate layer. Moreover, the involved mesoporous SiO2 cores were responsible for the optimized abrasive–wafer interface contacts and the eliminated surface damages. As expected, the proposed abrasive system enabled the nearly scratch-free and atomically planarized surfaces with angstrom-level finish (∼0.14 nm Ra, ∼0.18 nm Rq, ∼0.21 nm Rz), and simultaneously offered a ca. 63.8% of removal efficiency enhancement in PCMP compared to conventional CMP.