We have investigated the electronic structures of Pt/Y 3 Fe 5 O 12 (YIG) bilayers (prototypical spin-Seebeck devices), by means of hard X-ray photoelectron spectroscopy (HAXPES) using synchrotron radiation to reveal the detailed core-level electronic structures near the surface and interface that impact on unconventional magnetotransport properties in Pt/YIG systems. The PES spectra of Fe 2p, Y 3s and O1s suggest a chemical reaction at the interface between Pt and YIG. The Fe 1s spectra show the two kinds of valence states of Fe ions. The one is Fe 3+ in the YIG substrate, while the other is metallic Fe (Fe 0). In addition, the Fe 0 species are found to exist near the surface of the Pt layer. These results are consistent with the proposed origin of the anomalous properties, i.e., the presence of Fe impurities for a skew scattering.