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Electrochemical methods (cyclic voltammetry (CV), potential steps, and electrochemical impedance spectroscopy) were successfully combined with in situ reflectometry measurements for a detailed analysis of the passive layer evolution as a function of the electrode potential. Interestingly, both EIS and surface reflectivity allowed a film thickness in the nanometer range to be readily determined. In addition, transient analyses of the reflectivity simultaneously recorded with CVs show the formation of both Fe 2 O 3 and Fe 3 O 4 oxides. The image analysis showed that the steel surface reactivity is heterogeneous and presents micrometric islands coated with a thicker oxide layer than the surrounding surface. The in situ combination of these techniques thus offers a powerful analytical description of the interface on a local scale and its transient response to a perturbation.