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Single‐step conversion of methane to methanol in the gaseous phase is required for high value added application of methane and environmental protection, but it is challenging. Here, direct oxidation of methane to methanol under gaseous condition on iridium promoted Cu/CeO2 catalyst, prepared using a sol‐gel method, is investigated. The addition of iridium can effectively upgrade the redox properties and oxygen storage capacity due to intense metal interaction, stimulating a prominent catalytic performance for methane conversion to methanol on Cu−Ir@CeO2 catalyst. Approximately 26.2 μmol/gcat methanol yield and 68 % methanol selectivity are achieved on the trimetallic 5Cu0.5Ir@CeO2 catalyst at 550 °C in 2 h. Consequences of the analysis of XRD, SEM, HRTEM, Raman, FI‐IR and XPS demonstrate that highly‐dispersed Ir and Cu species are uniformly distributed on CeO2 surface, and partial Cu or Ir atoms replace Ce4+ in CeO2 lattice due to the metal interaction in the colloidal structure, which can impact the catalyst's electronic properties. H2 temperature‐programmed reduction (H2‐TPR) and CH4 temperature‐programmed desorption (CH4‐TPD) results disclose that the unique ternary surface exhibits excellent redox properties and strong adsorption capacity for methane, which can activate the first C−H bond of methane to methyl species, and then react with OH− to form methanol. The good stability in cyclic operation is an additional attribute, rendering this type of catalyst a "front‐runner" in future catalyst development for direct methane‐to‐methanol. This composite catalyst design provides hope for developing ternary metal‐oxide catalysts for functionalization of methane. [ABSTRACT FROM AUTHOR]