A partially ordered Fe16N2 thin film, which exhibits a higher saturation magnetization than a bcc-Fe thin film, was grown on a Au(001) texture on a GaAs(001) substrate for studies of crystalline structure, electronic structure, and magnetic properties. Fe 2p3/2 and 2p1/2 X-ray photoelectron spectroscopies (XPS) reveal the electronic hybridization between the Fe atoms and the adjacent N atoms, whereas a multipeak analysis suggests the charge-transfer-induced electronic rearrangement of electronic configuration in Fe(8h) and Fe(4e) geometrical sites. These results are consistent with the previous model and help explain the saturation magnetization enhancement in the α-FeN system.