X-ray photoelectron spectroscopy (XPS) of five-monolayer-thick ZrO2 films reveals a core level binding energy difference of up to 1.8 eV between the tetragonal and monoclinic phase. This difference is explained by positively charged oxygen vacancies in the tetragonal films, which are slightly reduced. Due to the large band gap of zirconia (≈5-6 eV), these charges shift the electron levels, leading to higher binding energies of reduced tetragonal films w.r.t. fully oxidized monoclinic films. These core level shifts have the opposite direction than what is usually encountered for reduced transition metal oxides. The vacancies can be filled via oxygen spillover from a catalyst that enables O2 dissociation. This can be either a metal deposited on the film, or, if the film has holes, the metallic (in our case, Rh) substrate. Our study also confirms that tetragonal ZrO2 is stabilized via oxygen vacancies and shows that the XPS binding energy difference between O 1s and Zr 3d solely depends on the crystallographic phase.