At ambient temperature and pressure. C2H2 and H2 are the dominating products from pure methane conversion under corona discharge (PCD). When the energy density of 194-1788 kJ/mol was applied, 7%-30% of C2H2 yield and 6%-35% of H2 yield per pass have been obtained. These resuits are higher than the maximum thermodynamic yield of H2H2 (5.1%) and H2 (3.8%) at 100 kPa and 1100 K, respectively. Thereby, pulsed corona discharge is a very effective tool for “beyond-thermal-equilibrium” conversion of methane of C2H2 and H2 at ambient temperature and pressure. In the PCD energy density range of 339-822 kJ/mol, the carbon distribution of the methane conversion products is found to be: C2H2 86%-89%, C2H6 4%-6%, C2H4 4%-6%, C3～2%, C4～1%. Through comparison of the product from pure methane, ethane and ethylene conversion at the same discharge conditions, it can be concluded that three pathways may be responsible for the C2H2 formation via CH, radicals produced from the collisions of CH4 molecules with energized electrons in the PCD plasma: (i) C2H2 is formed directly from free radical reactions, (ii) C2H2 is formed through the dehydrogenation of C2H2, which is formed via free radical reactions primarily, and (iii) C2H6 is the primary product and then dehydrogenates to C2H4 (secondary product) and followed by C2H4 dehydrogenation to C2H2.