X‐ray absorption near edge structure (XANES) spectra in soft X‐ray region were utilized for the characterization of Zn1‐xMgx O films. Zn L ‐edge XANES spectra of Zn1‐xMgx O films changed as increasing Mg composition x, suggesting that local structure of the Zn atom in ZnO was influenced by the alloying with MgO. Mg K ‐edge XANES spectra of Zn1‐xMgx O films did not show any dependence on growth methods, but was different from that of MgO bulk, showing 4‐fold symmetry of Mg atoms. Similarly, O‐K edge XANES spectrum in Zn1‐xMgx O film showed 4‐fold symmetry of O atoms, and depicted a slight difference from that of ZnO, probably due to the contribution of 6‐fold Mg‐O bond formation. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)