Five copper zinc thiolate complexes (iPr(3)PCu) 2(ZnEt2)(edt) (1-Et), (iPr(3)PCu) (2)(Zn(iPr) (2))(edt) (1iPr), (iPr(3)PCu)(4)(edt)(2)(ZnMe2) (2), (iPr(3)PCu)(3)(ZnPh2)( ZnPh)(edt)(2) (3), and (iPr(3)PCu) Zn-2(2)(edt)(3) (4) were prepared by the reaction of (iPr(3)PCu)(2)(edt) with ZnR2 (R= Me, Et, Ph, iPr) with or without addition of ethanedithiol (edt(2-) = ethane- 1,2-dithiolate). The molecular structures of these complexes were determined by single crystal X-ray diffraction. The ethanedithiolate ligands coordinate in mu 3- eta(1):eta(2):eta(1) (2, 4), mu 4- eta(1):eta(1):eta(2):eta(1)(1-R, 3) and mu 5-eta(1):eta(1):eta(2):eta(1):eta(1)(2) bridging modes, each sulfur atom binds to two or three metal atoms. Evidence for the presence of the weak Zn-S bonds in solution was provided by NMR spectroscopy. Mixtures of 1-Et, 1-iPr, or 3 with Sn(edt)(2) were examined by thermogravimetry up to 600 degrees C, whereupon volatile thermolysis products were identified by mass spectrometry. In all thermolysis experiments, the formation of Cu2ZnSnS4 as main product, besides small amounts of binary metal sulfides, was confirmed by Xray powder diffraction (PXRD) and EDX (energy dispersive Xray spectroscopy) analysis.