Abstract Cerium dioxide (CeO 2 ) has huge potential in many applications ranging from biochemical engineering to the coating industry. Here, the first example of visible light photo‐mediated Pickering emulsion polymerization of (meth)acrylate monomers is reported using CeO 2 nanoparticles (NPs) as solid stabilizer. A ω,ω′−dicarboxylic acid diphenyl disulfide photoinitiator is anchored on the surface of the CeO 2 NPs and used to initiate the emulsion polymerization of methyl methacrylate (MMA) and of MMA/ n ‐butyl acrylate (MMA/BA) under visible light leading to CeO 2 ‐armored latexes. Radicals generated upon light irradiation trigger the formation of polymer chains chemically attached to the CeO 2 NPs, promoting their subsequent adsorption on the latex surface. The composite films obtained from the CeO 2 ‐armored P(MMA‐ co ‐BA) latexes exhibit a unique honeycomb nanostructure with the nanoceria located in the walls giving the materials excellent mechanical, anti‐UV, and photocatalytic properties.