The use of several soluble metal polychalcogenides to prepare solid state materials is presented. Thermal gravimetric analysis (TGA) data, under inert atmosphere, of the molecular compounds (Ph4P)2[Cd(Se4)2], (Ph4P)4[Cu2Se14], (Ph4P)2[Cu4Se12], (Ph4P)4[In2Se21] and (Et4N)3[M3Se15], (M=In, TI), show that the corresponding binary solid state compounds are formed as single phases at temperatures as low as 530°C. We have grown films of CdSe, Cu2-xSe, β-In2Se3, TISe and CuInSe2 using these complexes as precursors. The films were prepared by pyrolysis of green precursor films, cast from DMF solutions. CuInSe2 was prepared by co-thermolysis of Cu/Sex and In/Sex complexes. The chemical, X-ray, spectroscopic and electron microscopic characterization of these molecular precursor-derived films as well as their charge transport characterization is reported.