Abstract Complexes of Sn(II), Sn(IV), Ge(IV), and Si(IV) with the ambidentate pyridine-2-thiolato ligand (PyS-) were synthesized and characterized by multinuclear NMR spectroscopy and single-crystal X-ray diffractometry. Comparison of the structures of E(PyS)2Cl2 (E=Sn, Ge, Si) and E(PyS)4 (E=Sn, Si) allows for insights into the group 14 coordination chemistry of this ambidentate chelator in dependence