Catalysts for dehydrogenative conversion of methane (DCM) to higher hydrocarbons are worthy of attention. Indium supported on silica (In/SiO2) was found for effective catalyst for the DCM reaction above 1023 K. Products were ethane, ethylene, acetylene, propylene, benzene, toluene, naphthalene and hydrogen. A highest selectivity of sum of products was 96 % at 1098 K and a steady‐state sum yield was 2.1 % with 63 % selectivity at 1173 K. Characterization studies using temperature‐programed X‐ray diffraction (TP‐XRD) and scanning electron microscopy (SEM) indicated that the working state of indium catalyst was liquid metal. Effects of reaction temperature on the product distribution and studies of temperature‐programed‐reaction (TPR) indicated that liquid‐metal indium activated methane and selectively converted to ethane. Higher hydrocarbons were produced from ethane in the gas phase without catalyst.