The caged photoluminescence compound 2-(2'-benzoylphenyl)benzoxazole (BzPO) modified with poly(N,N-dimethylacrylamide) was synthesized. Transparent polymer hybrids with the obtained polymer were prepared by using hydrogen bond interactions between amide groups of the organic polymer and silanol groups resulting from hydrolysis of tetramethoxysilane. By UV irradiation upon the obtained polymer hybrids, the cage-released reaction of BzPO quickly took place even in a silica gel matrix, and the resulting polymer hybrids showed strong green photoluminescence deriving from a phototautomer of 2-(2'-hydroxyphenyl)benzoxazole (HPBO) dye. The preparation of "photoresist-like" photopatterning polymer hybrids could be also accomplished by using a photomask during UV irradiation. Furthermore, the photoluminescence of the polymer hybrids was reversibly quenched and emitted by the recaging of the hydroxyl group of HPBO with adsorption and desorption of water molecules. The miscibility of polymer hybrids depending on UV irradiation was evaluated by SEM and nitrogen adsorption porosimetry studies.