The detailed catalytic mechanism of a series of paddlewheel complexes [Mo2L4] featuring Mo-Mo quadruply-bond on radical addition of CCl4 to 1-hexene was studied using density functional theory. Different ligands of Mo-Mo bond are investigated to illustrate the ligand effect on the catalytic activity. The results show that the Mo-Mo quadruply-bond paddlewheel complexes have high catalytic activities on the title reaction. The whole reaction involves 4 steps. Firstly, the C-Cl bond of first CCl4 is activated by [Mo2L4] catalyst, and [Mo2L3Cl] and CH3COOCCl3 are obtained. Then the second CCl4 adds to [Mo2L3Cl] to produce [Mo2L3Cl2] and·CCl3 radical;·CCl3 radical interacts with 1-hexene to get an addition, the addition product which reacts with one Cl atom of [Mo2L3Cl2] to get the last product nBuCHClCH2CCl3 and regenerate [Mo2L3Cl]. The addition of the first CCl4 to [Mo2L4] catalyst is the rate-determining step of the whole reaction. Because this step is not in the catalytic cycle, the reaction would speed up after a certain period of time. The catalytic activity of dimolybdenum paddlewheel complex is depended on the natural population analysis (NPA) charge of Mo and the redox potential E(Mo24+/Mo25+). The higher NPA of Mo atom and higher E(Mo24+/Mo25+) of the catalyst, the higher catalytic activity it has. Our results provide an explanation for experimental observations and useful insights for further development of bimetallic catalysts in radical addition reactions.