We report the first study of optical emission and excitation properties from interband transitions both in the oxygen-plasma-anodised film (ODA) on Ge [111] and vitreous germanium dioxide. Seven optical emission (EM) structures ranging from 2.85 eV to 4.20 eV were obtained using cathodoluminescence (CL) and photoluminescence (PL) methods. PL excitation (EX) spectra obtained have also demonstrated that the eleven absorption transitions are related to the EM bands.