Electrochemical behaviour of bare niobium and-phosphoric acid anodized niobium electrodes is investigated in nitric acid solutions. Electrochemical impedance spectroscopy and polarisation techniques have been used to investigate the open-circuit growth of the passive film. The stability of the anodic oxide film has been studied as a function of the formation voltage, formation current density and concentration of the ambient electrolyte. The results show that the Nb-Nb2O5-1M HNO3 does not behave as a perfect dielectric. The flat band potential and donor concentration of the semiconducting anodic oxide film have been calculated from the Mott-Schottky plots.