The new selenophosphate phases A0.7Bi1.1P2Se 6 (A = Cu, Ag) and CuBi1-X SbX P2Se 6, stabilized by the chalcophosphate anions (P2Se6)4-, were prepared by molten polythiophosphate fluxes. The reaction products were characterized by atomic absorption (ICP) and Scanning Electron Microscopy (SEM-EDX), powder X-ray (XRD), Fourier transform infrared spectroscopy (FTIR) and a.c. and d.c. electrical conductivity measurements. The phases A0.7Bi1.1P2Se 6 and CuBi1-X SbX P2Se 6 are structurally related to AMP2Se6 and they possess two-dimensional (2D) structure. These phases are semiconductors, with values of electrical conductivity, sI, about 10-4 W-1cm-1 at room temperature