The data on electrical and photoelectric characteristics of Ga2O3/ZnGeP2 hetero-structures formed by RF magnetron sputtering Ga2O3 target with a purity of (99.99%) were obtained. The samples are sensitive to UV radiation with a wavelength of λ = 254 nm and are able to work offline as detectors of short-wave radiation. Structures with Ga2O3 film that was not annealed at 400 °C show weak sensitivity to long-wavelength radiation, including white light and near-IR (λ = 808 and 1064 nm). After annealing in an air environment (400 °C, 30 min), ZnGeP2 crystals in contact with Ga2O3 show n-type conductivity semiconductor properties, the sensitivity of Ga2O3/ZnGeP2 hetero-structures increases in the UV and IR ranges; the photovoltaic effect is preserved. Under λ = 254 nm illumination, the open-circuit voltage is fixed at positive potentials on the electrode to Ga2O3, the short-circuit current increases by three orders of magnitude, and the responsivity increases by an order of magnitude. The structures detect the photovoltaic effect in the near-IR range and are able to work offline (remotely) as detectors of long-wavelength radiation.