The characteristics of copolymerization of 5-vinyl-2- norbornene and tert-butyl methacrylate by Fe(acac)3-Al(i-Bu)3 and the structure of the copolymer are presented in the paper. All polymerization reactions were carried out under nitrogen atmosphere using syringe technic. The copolymer is characterized by IR、NMR and element analysis. The copolymerization can be performed in the solvents such as aromatic hydrocarbon. The suitable Al/Fe molar ratio is 23. The molecular weight distribution is Mw/Mn=1.18-1.39, The molecular weight of copolymer is changed with the change of ENB/TBMA molar ratio. 5-vinyl-2- norbornene and tert-butyl methacrylate are 45.5% and 55.5%, respectively in the copolymer. The third composition exerts influence on the copolymerization. The yield of copolymer are lower with the third composition than that without the third composition. The copolymerization can be obtained at room temperature, however, the increasing reaction temperature causes an increase of the copolymer yield. The yield of copolymer is changed with the change of Al/Fe molar ratio. The suitable Al/Fe molar ratio is 23.