Copper-oxide compound semiconductors provide a unique possibility to tune the optical and electronic properties from insulating to metallic conduction, from bandgap energies of 2.1 eV to the infrared at 1.40 eV, i.e., right into the middle of the efficiency maximum for solar-cell applications. Three distinctly different phases, Cu2O, Cu4O3, and CuO, of this binary semiconductor can be prepared by thin-film deposition techniques, which differ in the oxidation state of copper. Their material properties as far as they are known by experiment or predicted by theory are reviewed. They are supplemented by new experimental results from thin-film growth and characterization, both will be critically discussed and summarized. With respect to devices the focus is on solar-cell performances based on Cu2O. It is demonstrated by photoelectron spectroscopy (XPS) that the heterojunction system p-Cu2O/n-AlGaN is much more promising for the application as efficient solar cells than that of p-Cu2O/n-ZnO heterojunction devices that have been favored up to now.