Photo-patterning iron iron oxide particles derived from Fe(CO)5 adsorption on to porous Vycor glass (PVG) yield refractive index gradient capable of guiding, focusing and diffracting light. The present study focuses on the charge state and local structure of the photo-deposited iron and their cross sectional distribution with in the porous matrix. High resolution XAFS corroborate previous Mossbauer studies, which indicated Fe(0) and Fe(III). XANES pre edge analysis confirms Fe(III) and no formation of Fe(II). Elemental iron found in the PVG immediately after photolysis is concentrated in the interior of the glass. Although some elemental iron is found on the surface of the glass they are covered with a protective layer of Fe(III). This protective layer is strong enough to prevent further oxidation of elemental iron particles during the annealing process at 650C. The elemental iron found in the interior of the glass oxidized during the annealing process until the protective layer of Fe(III) is formed. The results suggest that once the Fe(III) / Fe(0) ratio reaches a critical value further oxidation is prevented.