A ketocyanine ligand containing two N-aza-15-crown-5 residues has been synthesized and covalently anchored to a silica substrate through an azomethine link. The ligand formation and molecular structure have been determined by combining spectral data and molecular simulations. Preferential adsorption of rare-earth metals from aqueous solutions to the modified surface has been noticed. In the case of lanthanum, the adsorption is accompanied by significant fluorescence enhancement, which allows this system to be used as a sensor for La3+ion.