Copper selenides were prepared in orthorhombic and cubic phases by electroless deposition. The photoresponses of these samples were measured, and the orthorhombic phase showed the highest photoresponse. It is further increased by treating the sample with Ru3+. Measurement of the resistivity of the two phases shows that the cubic phase is metallic. Mott-Schottky plot and resistivity measurements were used to construct the band diagram.