We next studied reactivity of the 16 stable SAAs as catalysts for direct methane conversion to ethane, ethylene, and acetylene, including the mechanisms of CH4 dehydrogenation and three C-C coupling steps. We observed that the outer-shell d electron configurations of dopants in SAAs play a critical role in determining both reactivities of CH4 dehydrogenation and C-C coupling steps but affect the two chemistry in a different way. Basically, SAAs with dopants from early and midrow transition metals favor C-H bond activation, while SAAs with dopants from late transition metals favor C-C coupling. By performing quantitative selectivity analysis, we identified that Ni/Cu SAA, Rh/Cu SAA, and Cr/Cu SAA exhibit high activity and selectivity towards generating multi-carbon hydrocarbons based on thermodynamics favorability.