A new method for anchoring the metallocene catalyst on macroreticular resin support was developed. Functionalized 20% cross-linked PVBC (polyvinylbenzylchloride or chloromethylated polystyrene) with functional group (diethanolamine, -N(CH2CH2OH)2) was used as macroreticular resin support (P), which was further used to prepare the supported Cp* TiCl3 catalyst (Cp*TiCl3/P). The activity of Cp*TiCl3/P catalyst was comparable to or higher than that of homogeneous counterpart. The molecular weight and melting temperature of polymer obtained with the supported catalysts were much higher, and they were not affected significantly by polymerization conditions such as amount of cocatalyst polymerization temperature and ethylene pressure. FT-IR and CP/MAS 13C NMR spectroscopy were used to investigate the nature of active species of Cp*TiCl3/P catalyst. Although the homogeneous Cp*TiCl3 exhibited extremely low catalytic activities for ethylene/1-hexene copolymerization, however, the polymer supported catalysi (Cp*TiCl3/P) showed the remarkable activity with improved 1-hexene incorporation. In addition the synergetic effect (increase in the activity) upon the presence of 1-hexene was also observed in this catalysis.