The MnOx-Na2WO4 catalyst for oxidative coupling of methane (OCM) is highly attractive but its high light-off temperature (>800 °C) is a major obstacle for commercialization. In-depth understanding of reaction light-off relevant chemistry is particularly desirable. We explored the OCM light-off over several metal-oxide-supported MnOx-Na2WO4 catalysts. As CH4 conversion above 15% with acceptable C2-3 selectivity is considered as the sign of OCM light-off, support-dependent OCM light-off is clearly observed over MnOx-Na2WO4 supported on SnO2 (660 °C), TiO2 (670 °C), MgO (690 °C), and ZnO (720 °C), being tightly linked with the redox rate of Mn3+(or Mn4+) ↔ Mn2+ cycle governed by support oxides.