Developing effective iron-incorporated zeolites and determining their active centers for the direct oxidation of CH4 to oxygenates have remained challenging topics so far. In this paper, we successfully prepare the highly-dispersed iron supported Y zeolites by a facile solid-state ion-exchange method with ferrocene, which was conducted under water-free conditions followed by a series of calcination. Moreover, extra-framework dinuclear Fe2+ complexes are identified as so-called active alpha-iron sites on zeolites. ICP-OES, N-2 adsorption-desorption test, X-ray diffraction, solid-state Al-27 NMR, N2O titration, TEM. EPR and Fe-57 Mussbauer spectra were carried out to characterize properties of sample structure, acid sites, as well as the supported iron species. Characterization results indicate that high-temperature treatments have no effect on the typical structure feature of zeolites. Compared with catalysts synthesized by conventional impregnation, the samples prepared by the facile approach possess abundant dinuclear Fe2+ complexes but no Fe2O3 bulks and show weak acidity. These lead to a higher oxygenate selectivity in CH4 oxidation to oxygenates. Remarkably, the oxygenate (HCHO and CH3OH) selectivity of 6.5% at 375 degrees C can be eventually obtained. (C) 2018 The Chemical Industry and Engineering Society of China, and Chemical Industry Press. All rights reserved.