This paper discusses the application of the recently introduced mixed-conduction model (MCM) to describe the electrochemical behaviour of anodic films formed on Ni–Cr alloys. The MCM emphasises the coupling between the spatial distribution of ionic point defects in the film and the electronic conductivity of the film. The basic concepts of the MCM are introduced, and equations for the concentration profiles of ionic defects, for the conductivity and for the ac response of the film are derived. The experimental part of this work consist of characterising the anodic behaviour of Ni–Cr alloys, pure Ni and pure Cr in 0.1 M Na2B4O7 solution (pH 9.3) at ambient temperature using rotating disc and cyclic voltammetry, contact electric resistance (CER) and electrochemical impedance spectroscopic (EIS) techniques. The experiments indicate that the film on a Ni–20%Cr alloy resembles that on pure Cr, whereas similarities can be found between the film on Ni–10%Cr alloy and pure Ni. The conductivity of the passive film formed on Ni–Cr alloys can be concluded to be based on the spatial and potential distribution of the valence states of Ni and Cr in the film. In spite of several simplifying assumptions used in the simulations, a qualitative agreement between the theory and experimental data was achieved.