Single chamber electrochemical cells were fabricated by patterning working and counter electrodes of Ni and Pt on single-crystal Y2O3-stabilized ZrO2. Cells were characterized in mixed atmospheres of H2 and H2O at ratios of 1:1 and 1:20 at nominally 923 K and 67 Pa total pressure. Potential sweep and impedance measurements were conducted simultaneously with ambient-pressure x-ray photoelectron spectroscopy (APXPS), which is a unique synchrotron-based probe designed for in-situ chemical characterization of surfaces using photoemission at gas pressures large enough to achieve realistic densities of faradic current. Electrochemically induced oxidation of Ni was observed under anodic polarization and could be reversed by applying a cathodic bias. The thin-film microstructure could also be manipulated electrochemically in that pores exposing underlying electrolyte would open through the Ni film after polarization. Application of APXPS to resolve fundamental details of high-temperature electrochemical process in-situ is discussed.