Temperature-dependent cathodoluminescence spectra were measured from (001) unintentionally doped, (100) Si-doped, and (010) Mg-doped β-Ga2O3 substrates prepared by either the floating zone growth or edge-defined film-fed growth methods. Although β-Ga2O3 is expected to be an indirect bandgap material, direct Γ-Γ transitions were found to be dominant in the optical transmittance spectra. The substrates exhibited no near-band-edge emission and instead exhibited ultraviolet luminescence, blue luminescence (BL), and green luminescence bands. Since the BL intensity strongly depended on the resistivity in the crystals, there was evidence of a correlation between the BL intensity and formation energy of oxygen vacancies.