Polymeric encapsulation of a high surface energy inorganic can aid in its uniform dispersion in a composite coating. Here we systematically explored an approach to suitable encapsulation conditions for two specialized photoluminescent pigments. While a suspension‐like process was desired to polymerize the layer at the inorganic surface, the robustness of the encapsulation was insufficient. By way of a simplified silica analog, proper conditions were determined to covalently link p(methyl methacrylate‐co‐glycidal methacrylate) latex particles to the inorganic surface through silane coupling. Those conditions were then successfully leveraged to the irregularly shaped photoluminescent pigments without deleterious impact on phosphorescence emission spectra nor on the persistence of the emission.