A simple and effective way to prepare poly(acrylate)s, such as poly(methacrylate), poly(butyl acrylate) and poly(butyl methacrylate), has been achieved by using the single component aluminum-based compounds, such as modified methylaluminoxane (MMAO), triisobutylaluminium (TIBA) and triethylaluminium (TEA) as initiators. Effective initiations and high molecular weight polymers with unimodal molecular weight distributions could be easily obtained by varying the reaction parameters of systems under mild conditions. Although these aluminum compounds were inefficient initiators for methyl methacrylate (MMA) polymerization, they exhibited remarkable catalytic activity for butyl methacrylate (BMA) polymerization, affording high molecular weight poly(BMA)s.