Selective conversion of methane to value-added products with high activity and high selectivity to the target products under mild reaction condition remains a great challenge. Herein, bicomponent IrFe supported on ZSM-5 (IrFe/Z-5) was investigated for the selective oxidation of methane. Compared with the 0.7Fe/Z-5 catalyst, the 0.1Ir-0.6Fe/Z-5 exhibited much higher oxygenate yield (3192 vs 971 μmol/g/h). In addition, higher H2O2utilization efficiency was obtained, and the selectivity toward formic acid was enhanced from 54% to 71.3%. It was found that the activation of the C–H bond was improved by the introduction of Ir single atoms. The superior catalytic performance of 0.1Ir-0.6Fe/Z-5 can be attributed to the synergistic effect between Ir and Fe species with high C–H bond activation capacity and high H2O2utilization efficiency.