By reaction of Me3SiSBu with anhydrous tin(II) chloride bis(butylthio)tin was obtained that exemplified a coordination polymer [Sn(SBu)2] n , whose elementary unit contained according to X-ray diffraction study three independent four-membered rings Sn2S2 of unusual geometry. It was demonstrated that polymeric thiolates [E(SBu)2] n (E = Ge, Sn) readily reacted with TsiLi (Tsi = C(SiMe3)3) in a mixed solvent ether THF affording in a good yield ate-complexes [(Me3Si)3CE(μ-SBu)2Li(THF)2]. Both complexes contain a four-membered ring in a butterfly conformation where the lithium atom is symmetrically bonded to both sulfur atoms, and the coordination polyhedra of Ge and Sn atoms may be regarded as distorted tetrahedra AB3X, where one of coordination places is occupied by unshared electron pair. The structure of the ate-complexes observed in a crystal is conserved also in solution of nonpolar solvents.