An oxide semiconductor β-CuGaO2 with a wurtzite-derived β-NaFeO2 structure has been synthesized. Structural characterization has been carried out by Rietveld analysis using XRD and SAED, and it was shown that the lattice size is very close to that of zinc oxide. The optical absorption spectrum indicated that the band gap is 1.47 eV, which matches the band gap required to achieve the theoretical maximum conversion efficiency for a single-junction solar cell. The thermoelectromotive force indicated p-type conduction in its intrinsic state. Density functional theory calculations were performed to understand the electronic structure and optical properties of the semiconductor. These calculations indicated that β-CuGaO2 is a direct semiconductor and intense absorption of light occurs near the band edge. These properties render this new material promising as an absorber in solar cells.