Abstract: A series of N-methylimidazole-CuCl2 complexes CuLnCl2 (L = N-methylimidazole = N-Mim, n = 1, 2, 4) were synthesized from N-Mim and CuCl2?2H2O and characterized by XRD, FTIR and TG. The catalytic performance of CuLnCl2 in the synthesis of 2, 4, 4, 4-tetrachlorobutyronitrile (TBN) by atom transfer radical addition (ATRA) reaction of CCl4 and acrylonitrile (AN) were compared. The effects of reaction temperature, reaction time, catalyst dosage and synergistic catalytic effect of solvent on the yield of TBN were investigated. The results showed that the Cu active cen-ter constructed by the spatial coordination of CuL2Cl2 showed the best catalytic performance. Under the conditions of acetonitrile (MeCN) as solvent, n(CuL2Cl2)∶n(AN)=1∶1000，n(CCl4)∶n(AN)=1.1∶1，the yield of TBN could reach 91.6% at 100 ℃ for 9 h. After being reused for 4 times, and the activity of catalyst did not decrease significantly. Based on the relevant experimental results, the oxidation-reduction catalytic cycle mechanism of Cu(Ⅱ)/Cu(Ⅰ) in the ATRA reaction of CCl4 and AN catalyzed by CuL2Cl2 was proposed.