The oxide film formed on nickel base alloys at high temperature and high pressure water exhibits semi-conducting properties evidenced by photocurrent generation when exposed to monochromatic light. The use of macro- and micro-photoelectrochemical techniques (PEC and MPEC) aims to identify the different semiconductor phases and their distribution in the oxide film. Three different nickel base alloys were corroded in recirculation loop at 325 °C in pressurised water reactor primary coolant conditions for different exposition durations. PEC experiments on these materials enable to obtain macroscopic energy spectra showing three contributions. The first one, with a band gap around 2.2 eV, was attributed to the presence of nickel hydroxide and/or nickel ferrite. The second one, with a band gap around 3.5 eV, was attributed to Cr2O3. The last contribution, with a band gap in the range of 4.1–4.5 eV, was attributed to the spinel phase Ni1−xFexCr2O4. In addition, macroscopic potential spectra recorded at different energies highlight n-type semi-conduction behaviours for both oxides, Cr2O3 and Ni1−xFexCr2O4. Moreover, MPEC images recorded at different energies exhibit contrasted regions in photocurrent, describing the distribution of nickel hydroxide and/or nickel ferrite and Cr2O3 in the oxide film at a micron scale. It is concluded that PEC techniques represent a sensitive and powerful way to locally analyse the various semiconductor phases in the oxide scale.