The electrochemical promotion of the C2H4 + O2 total oxidation reaction over a Pt catalyst, interfaced to yttrium stabilized zirconia (YSZ), has been studied at 0.25 mbar and T = 650 K using near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) as an in situ method. The electrochemical promoter effect is linked to the presence of a several layers thick graphitic overlayer that forms on the Pt surface in the presence of C2H4. Our NAP-XPS investigation reveals that electrochemical pumping of the Pt/YSZ catalyst, using a positive potential, leads to the spillover of oxygen surface species from the YSZ support onto the surface of the Pt electrode. Based on the XP spectra, the spillover species on Pt is identical to oxygen chemisorbed from the gas-phase.