Abstract Sol–gel glasses with covalently linked lanthanide complexes are luminescent materials which can be processed at ambient temperatures, which have a good solubility and uniform distribution of the complexes in the host matrix. In this study, a luminescent terbium(III) complex was covalently coupled to an organic–inorganic hybrid material prepared by the sol–gel process. This was realised by use of nicotinate groups as the ligands for the terbium(III) ion. The [Tb(C 5H 4NCO 2) 3(phen)(H 2O) 2] complex was immobilised on the sol–gel glass matrix and showed a green photoluminescence upon irradiation with ultraviolet light. The nicotinate groups act as an antenna to absorb the incident light and channel the excitation energy to the terbium(III) ion. The sol–gel glass was also prepared for the corresponding europium(III) complex. In this case, excitation of the europium(III) ion was possible via both the nicotinate ligands and the 1,10-phenanthroline ligands. High-resolution luminescence and excitation spectra were recorded and the radiative lifetimes were measured.