Near-infrared (NIR) luminescent ternary and hydrated binary neodymium β-diketonates emitting at ca. 1330 nm are presented. The effects of ligand moieties on the photoluminescence properties of Nd 3+ ions are discussed. Moreover, the neodymium organic complex neodymium tris(2-theonyltrifluoroacetonate)bis(triphenylphosphine oxide), Nd(TTA) 3 (TPPO) 2 , which has the best photoluminescence properties among all investigated neodymium complexes, is incorporated into vinyltriethoxysilane-derived ORMOSIL (organically modified silicate) film by a multistep sol–gel process. The Nd doping concentration was up to 5 mol% related to Si. The spectroscopic results about as-doped ORMOSIL films indicate that the ligands around Nd 3+ ions indeed shield effectively Nd 3+ ions from luminescence-quenching impurities in the host matrix, such as OH groups.