Transparent conducting oxide (TCO)/hydrogenated amorphous silicon (a‐Si:H) interfaces are investigated combining kinetic ellipsometry and Kelvin probe measurements. It is shown that the correlation between both in situ techniques allows a detailed description of the optoelectronic behavior of these interfaces. The Schottky barrier at the TCO/a/Si:H interfaces, as revealed by Kelvin probe measurements, is correlated with the chemical reduction of the TCO surface during the early stage of a:Si:H growth, as evidenced by kinetic ellipsometry. In particular, indium tin oxide (ITO) and SnO2 are found to be reduced by the silane plasma at 250 °C. On the countrary, ZnO is found highly resistant upon plasma reduction. The influence of the substrate temperature during a‐Si:H deposition is analyzed. Finally, the technical consequences of this study are outlined.