Surface structures of iron–phosphate glasses were examined using X-ray photoelectron spectroscopy (XPS). Cr2O3, CoO, and Al2O3 were introduced to the glass by the replacement of a part of Fe2O3, and the simulated fission products are also added. The obtained glasses showed high chemical durabilities by MCC-1 test. In situ high-temperature and room-temperature XPS measurements were conducted on the polished sample surfaces and also those after 1-week chemical durability test. Unique trends were observed in XPS spectra on heating and after the chemical durability test, respectively. Nature of the glass surface of iron–phosphate glasses was explained from the point of view of surface energy, and the origin of high chemical durability and the effect of chromium ions were discussed based on the changes on surface composition and valence states of transition-metal ions.