摘要： This work shows the interest to use a real time, white laser-based ellipsometer to characterize a complex electrolyte|electrode interface during an electrochemical process in an aqueous-based medium. This method is proposed to probe electrochemical interfaces that are usually not suitable to the full extent application of ellipsometry due to great disturbance of the re?ected light ?ux provoked by gas evolution or roughness. In situ spectroelectrochemical ellipsometry combining such a visible super continuum ?ber laser-band source was not previously reported to the best of the authors’ knowledge. The setup was employed to monitor an electrochemical process whose mechanism was previously incompletely described: the prespark anodization regime of the plasma electrolytic oxidation process of the Mg alloy AZ91D in the 3M KOH electrolyte. Above the anodization voltage of 4 V, the side water oxidation reaction induced light diffusion that reduces re?ected light beam intensity. The process is monitored in an extended voltage range from 4 to 40 V and in an extended spectral range (495–800 nm). In the presented case, the use of a visible super continuum ?ber laser-band source enhanced the signal-to-noise ratio giving access to a deeper picture of the triplex layer structure during surface repassivation by monitoring the evolution of the outer, inner, and interfacial layers.