The influence of alloying elements on the electrochemical and semiconducting properties of thin passive films formed on several steels (carbon steel, ferritic and austenitic stainless steels) has been studied in a highly concentrated lithium bromide (LiBr) solution at 25°C, by means of potentiodynamic tests and Mott–Schottky analysis. The addition of Cr to carbon steel promoted the formation of a p-type semiconducting region in the passive film. A high Ni content modified the electronic behaviour of highly alloyed austenitic stainless steels. Mo did not modify the electronic structure of the passive films, but reduced the concentration of defects. •The addition of Cr to carbon steel promotes p-type semiconductivity.•Passive films formed on stainless steels are made up of complex spinel oxides.•Ni modifies the electronic behaviour of highly alloyed austenitic stainless steels.