Two new lanthanoid thiogermanates [Ln(dien)(2)(μ-η(1),η(2)-GeS(3)(SH))](n) {Ln = La(), Nd(); dien = diethylenetriamine} were solvothermally synthesized and structurally characterized. Both and represent the first examples of the soft Lewis basic [GeS(3)(SH)](3-) anions as tridentate bridging ligand to hard Lewis acidic Ln(3+) ions. Both and exhibit semiconducting properties with absorption band edges of 2.11 eV for and 2.28 eV for . The DFT study of indicates a direct band gap with an electronic transfer excitation of S 3p to both Ge 4s and La 5d orbital electrons.