The chiral Salen-type Schiff base ligand H 2 L (H 2 L = (s)-(+)2,2′-bis(2-hydroxy-3-methoxybenzylideneamino)-1,1′-binaphthyl), was selected to obtain the new chiral Cu2+ complex CuL (1), which was found to catalyze the polymerization of norbornene (NBE). The complex shows the distinctively distorted geometry from a square-planar reactive center, this feature being suggested to account for the efficient catalysis on the vinylic-type polymerization of NBE, with moderate molecular weights and narrow molecular weight distributions. From the involvement of a chiral Salen-type Schiff base ligand H 2 L (H 2 L = (s)-(+)2,2′-bis(2-hydroxy-3-methoxybenzylideneamino)-1,1′-binaphthyl), the new chiral Cu2+ complex CuL (1) was obtained, and found to catalyze the polymerization of Norbornene (NBE). The polymerization results showed that the Cu2+ complex 1, endowing the distinctive distortion from a square-planar reactive center, could efficiently catalyze the vinylic-type polymerization of NBE, with moderate molecular weights and narrow molecular weight distributions.