We report a theoretical study on the impact of native defects present in CuVO3 material on its conductivity using first-principles calculations based on density functional theory. We find a low and direct band gap of 1.4 eV for the pristine cell together with relatively high solar absorption efficiency, high macroscopic dielectric constant, and delocalized orbital characters of photogenerated charge carriers. This result highlights CuVO3 as a good candidate for photovoltaic application. Among the various explored native defects (including vacancies, interstitials, and antisites), we demonstrate that only those associated with O vacancies are shallow donors and with Cu vacancies are shallow acceptors, leading respectively to n-type and p-type conductivities under O-poor and O-rich growing conditions.