AbstractReactivity of methane and benzene over various metals supported on MFI zeolite was investigated in a wide range of temperature by a temperature‐programmed reaction method. The oxidation state was also analyzed, as supported by X‐ray absorption near edge structure (XANES). Pt, Rh, and Rh on MFI were reduced at <600 K, and showed high activity for both benzene methylation and methane dehydrogenation, and hence, low selectivity for the methylation at high temperature. The short catalyst life of Pt/MFI suggests deactivation due to carbonaceous produced by the dehydrogenation. The oxidation state of Co species on ion exchange site of MFI was kept at +II in the experimental range (<843 K), and relatively high selectivity was observed on Co/MFI even at high temperature. Stable oxidized state of Co species thus contributed to catalyze the target reaction (methylation of benzene with methane).