The near-edge X-ray absorption fine structure (NEXAFS) spectra of poly(phenyl thioether) polymers with pendant Fe(Cp) iron moieties have been recorded at the carbon Is, iron 2p, and phosphorus is and 2p edges. This study shows that solution photofragmentation of the organometallic polymer causes the removal of iron moieties and the preparation of the corresponding organic polymer: poly(phenyl thioether). Spectroscopic characterization of poly(phenyl thioether) prepared in this manner indicates the presence of iron oxide, likely Fe2O3, and hexafluorophosphate counterion trapped in the demetalated polymer matrix. A photolytic examination of the solid phase poly(phenyl thioether)-Fe(Cp) organometallic polymer shows that irradiation of this polymer in air leads to the formation of poly(phenyl thioether) and Fe2O3, while irradiation in vacuum leads to formation of iron species with a lower oxidation state. The ability to probe the oxidation state of this metal species is relevant to understanding how demetalation conditions affect the properties of the polymer.