Oxidative coupling of methane (OCM) catalyzed by MnOx‐Na2WO4/SiO2 has great industrial promise to convert methane directly to C2–3 products, but its high light‐off temperature is the most challenging obstacle to commercialization and its working mechanism is still a mystery. We report the discovery of a low‐temperature active and selective MnOx‐Na2WO4/SiO2 catalyst enriched with Q2 units in the SiO2 carrier, being capable of converting 23 % CH4 with 72 % C2–3 selectivity at 660 °C. From experiments and theoretical calculations, a large number of Q2 units in the MnOx‐Na2WO4/SiO2 catalyst is a trigger for markedly lowering the light‐off temperature of the Mn3+↔Mn2+ redox cycle involved in the OCM reaction because of the easy formation of MnSiO3. Notably, the MnSiO3 formation proceeds merely through the SiO2‐involved reaction in the presence of Na2WO4: Mn7SiO12+6 SiO2↔7 MnSiO3+1.5 O2. The Na2WO4 not only drives the light‐off of this cycle but also gets it working with substantial selectivity toward C2–3 products. Our findings shine a light on the rational design of more advanced MnOx‐Na2WO4 based OCM catalysts through establishing new Mn3+↔Mn2+ redox cycles with lowered light‐off temperature.
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