The complexes, [Cu{EC₅H₃(R-3)N}]₄ (E/R = Se/Me or Te/R; R = H or Me) were isolated by the reaction between CuCl and NaEC₅H₃(R-3)N and were characterized by elemental analyses, uv-vis and NMR (¹H, ¹³C) spectroscopy. The crystal structures of [Cu{SeC₅H₃(Me-3)N}]₄ and [Cu(TeC₅H₄N)]₄ revealed that the molecules are tetrameric in which each copper atom lies at the vertex of the tetrahedron and each face of the tetrahedron is capped by the bridging pyridylchalcogenolate ligand. Thermal behavior of these complexes was studied by thermogravimetric analysis. Depending on reaction conditions, thermolysis gave both stoichiometric and non-stoichiometric copper chalcogenides, which were characterized by XRD, EDX, SEM, TEM and SAED techniques. These precursors were used for the preparation of nanocrystals and for deposition of thin films of copper chalcogenides by AACVD (Aerosol Assisted Chemical Vapor Deposition).