In the search of new multifunctional molecular materials, the present paper introduces the work performed with the Salen-type Schiff base: bis-N,N′-p-bromo-salicylideneamine-1,2-diaminobenzene (H2bsph), to attain novel coordination complexes containing lanthanides centers (LnIII). So far, our studies have shown that the combination in acetone of the well-known H2bsph ligand, a base and NdIII(NO3)3·6H2O, results in a yellow solid which crystalline forms has been suitable for X-ray diffraction studies. As a result, a novel NdIII system has been achieved, with formula [Nd2(bsph)3(H2O)]·2CH3Cl (1). The architecture of 1 encloses two metal centers inserted among three Schiff bases (2NdIII:3(bsph2−)) resembling a sandwich-shape, is a rare example of triple-decker coordination species with only few similar systems described in the literature. The magnetic properties of 1 have been examined as well as the luminescence activity; the latest was compared with H2bsph for better interpretation.