Imine macrocyclic ligand (M-I) was used in conjunction with CuBr as novel catalytic system in atom transfer radical polymerization (ATRP) of methylmethacrylate (MMA), butylmethacrylate (n-BuMA) and 2-dimethylaminoethylmethacrylate (DMAEMA). Two different initiators were involved such as Br-methoxypolyoxy-ethylene macroinitiator and 1, 3, 5-(2-bromo-2'-methylpropionato) benzene three arm star initiator. The polymerization reactions were conducted at 90 degrees C in toluene. The macrocyclic ligand M, demonstrated peculiar behavior which was monitored by the GPC measurements whether with respect to the polydispersities or the molar masses. High molar masses than expected were obtained except incase of DMAEMA monomer. The structures of the formed polymers were proven via (HNMR)-H-1.