Polymerizations of methyl methacrylate (MMA) monomer initiated by a novel Ni(II)alpha-benzoinoxime complex have been achieved under homogeneous conditions in the 25-60 degrees C temperature range. The activity for polymerization increases with reaction temperature and by carrying out the polymerization in solution of low-polarity solvents without any induction time. The obtained polymers have weight-average molecular weights about 105 and slight broad polydispersity indexes (2.2 <= M-w /M-n <= 3.3). Dependence of rate constants polymerization and decomposition of initiator (k(app) and k(d), respectively) on temperature was investigated and activation parameters were computed from Arrhenius plot. H-1-NMR analysis of PMMA revealed a syndio-rich atactic microstructure in agreement with conventional radical process. Radical scavenger TEMPO effect together with microstructure and molecular weight distributions data supported that the polymerization proceed via free radical mechanism. (c) 2008 Wiley Periodicals, Inc.