The C-H activations of methane, ethane, propane, and propene catalyzed by all-metal aromatic complexes Al4Fe were investigated. The results reveal that the rate-determining barrier of methane activation reaction with Al4Fe is lower than that of both some well-known inorganic catalysts and some metal organic catalysts. It was found that the all-metal aromatic complexes have high reactivity for the C-H activation of ethane, propane, and propene. Further research showed that the ability of all-metal aromatic complex to accept an electron and the degree of electron delocalization on its aromatic plane had obvious influences on the reactivity of Al4Fe. The present work predicts a new kind of catalyst for the alkyl C-H activation reaction: all-metal aromatic catalyst.