A luminescent thin film, Eu@glass, has been prepared on the surface of glass substrates from a silylated diamidopyridyl ligand L and the complex [Eu(dbm)3(H2O)2] (Hdbm=dibenzoylmethane) via a sol–gel method. The Eu@glass exhibits intense red photoluminescence under the irradiation of near UV light with a quantum yield of 26%. Compared to the compound [Eu(dbm)3(H2O)2], the photoluminescence intensity of Eu@glass is dramatically enhanced, and the emission lifetime of EuIII (0.517ms) is more than an order of magnitude longer.