Heterometal binuclear complexes, [CuLn(fsaen)(H2O)n](NO3) (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; n=4–5) and [CuLn(fsapn)(H2O)4](NO3) (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, or Dy) have been synthesized and characterized, where H4fsaen and H4fsapn denote N,N′-bis(3-carboxysalicylidene)ethylenediamine and N,N′-bis(3-carboxysalicylidene)-1,2-propanediamine, respectively. The ligand field band due to the copper(II) ion bound to the N2O2-site is at 18.5×103–19.5×103 cm−1 for [CuLn(fsaen)(H2O)n](NO3) and 18.4×103–19.2×103 cm−1 for [CuLn(fsapn)(H2O)4](NO3), which are higher frequencies than those of the mononuclear complexes, [Cu(H2fsaen)](H2O)0.5 and [Cu(H2fsapn)](H2O)0.5 (18.3×103 and 18.4×103 cm−1, respectively). When the complexes are dissolved in pyridine (Py), dimethyl sulfoxide (DMSO), or N,N-dimethylformamide (DMF), the d–d band frequency decreases in the order of the solvent DMSO>DMF>Py for the binuclear complexes, whereas it decreases in the order of DMF>DMSO>Py for the mononuclear complexes. These trends were discussed in terms of the different affinities of solvent molecules for copper(II) and lanthanoid(III) ions. No significant magnetic spin-exchange interaction occurred between metal ions.