Polymer composite materials based on CuS/ (CDS), Cu2S/(CDS) and Ag2S/(CDS) were obtained by substitution of Cd with Ag, Cu (II) and Cu (I) ions in the (CDS) rodlike nanocrystalline and investigated their electrophysical properties. It was found that the electrical conductivity of CuS/(CDS) heterostructure is in five orders higher compared to the (CDS). It was shown that the values of the complex permittivity at identical content of CuS and Cu2S nanoparticles are more than 40 % higher for the 0.3 Cu2S/(CDS)PVDF system in comparison with the 0.3 CuS/(CDS)-PVDF.