The synthesis, characterization, photoluminescent (PL) and electroluminescent (EL) behavior of trivalent Sc, Nd, Gd, Er, Tm and Yb complexes with 3-(5-methylbenzoxazol-2-yl)naphthol (L-5Me) and 3-(6-methylbenzoxazol-2-yl)naphthol (L-6Me) ligands are reported. An X-ray analysis of Sc(L-5Me)₃, Sc(L-6Me)₃ as well as the non-methylated analogue Sc(L)₃ has shown the monomeric structure of the complexes whereas the lanthanide naphtholates according to LDI-TOF data are dimers Ln₂(L-5Me)₆ and Ln₂(L-6Me)₆. The scandium complexes under photo- and electroexcitation revealed intense ligand-centered luminescence peaked at 522 nm. The PL and EL spectra of Nd, Tm and Yb compounds displayed moderate ligand-centered emission along with narrow bands of corresponding f–f transitions.