Chemical analysis of solid-liquid interfaces under electrochemical conditions has recently become feasible due to the development of new synchrotron radiation techniques. Here we report the use of "tender" X-ray ambient-pressure X-ray photoelectron spectroscopy (APXPS) to characterize a thin film of Ni-Fe oxyhydroxide electrodeposited on Au as the working electrode at different applied potentials in 0.1 M KOH as the electrolyte. Our results show that the as-prepared 7 nm thick Ni-Fe (50% Fe) film contains Fe and Ni in both their metallic as well as oxidized states, and undergoes further oxidation when the sample is subjected to electrochemical oxidation-reduction cycles. Metallic Fe is oxidized to Fe3+ and metallic Ni to Ni2+/3+. This work shows that it is possible to monitor the chemical nature of the Ni-Fe catalyst as a function of potential when the corresponding current densities are small. This allows for operando measurements just above the onset of OER; however, current densities as they are desired in photoelectrochemical devices (∼1-10 mA cm-2) could not be achieved in this work, due to ohmic losses in the thin electrolyte film. We use a two-dimensional model to describe the spatial distribution of the electrochemical potential, current density, and pH as a function of the position above the electrolyte meniscus, to provide guidance toward enabling the acquisition of operando APXPS at high current density. The shifts in binding energy of water with applied potential predicted by the model are in good agreement with the experimental values.