Chemical and electronic properties of ion beam synthesized Fe-Si binary structures are studied using X-ray photoelectron spectroscopy binding energy analysis. Ferromagnetic Fe-Si (Fe 3 Si) binary structure formation is enhanced in the ion-beam synthesis process by applying an in situ external magnetic field parallel to the Si substrate during the Fe implantation. Core-level analysis shows features corresponding to chemical environments of different Fe-Si phases. Fe 2p 3/2 and Fe 3s peaks were analyzed, considering peak position, symmetry, and splitting. The ferromagnetic Fe 3 Si phase shows a highly asymmetric 2p 3/2 peak at 706.6 eV and peak splitting in the 3s peak due to the exchange interaction with unfilled 3d electrons in the valance band. In contrast, the Si core-level did not show any significant features leading to the identification of Fe-Si binary compounds. The Si 2p peak showed a constant 0.2 eV peak shift toward the high-energy side compared to the elemental Si. Further valance band spectra reveal distinct features to help identify the Fe 3 Si phase. In general, core and valance band features of Fe-Si binary compounds provided definitive information about Fe 3 Si phase identification and its electronic structure with direct evidence of the exchange interaction, which occurs between core levels, valance band, and the unfilled 3d shell.