Thin films (~100 nm) of hetero-ligand complex compounds of terbium(III) with 3,5-dieethyloxybenzoic, 2,5-dimethyloxybenzoic, 3,4-dieethyloxybenzoic acids and phenanthroline as well as a uniform ligand complex of terbium(III) with 3,4-dieethyloxybenzoic acid, have been obtained. Using the data of electron and optical microscopy it has been found that during the process of film formation, the complex crystallizes. With the aim of improving the quality of a film surface, the complexes have been doped to a polymer matrix of poly-N-vinylcarbazole with the weight ratios from 1:1 to 10:1. On the basis of the dependence of the integral intensity of film luminescence on the weight ratio of components in it and also on the basis of kinetics of film luminescence, the assumption has been made about the polymer participation in excitation of luminescence of complexes in the film.