Abstract Polymerizations of methyl methacrylate with (α‐diimine)nickel(II)/methylaluminoxane (MAO) and (pyridyl bis(imine))iron(II) and (pyridyl bis(imine))cobalt(II)/MAO are reported. Effects of structural variation of the ligand on the activities of catalysts and polymer microstructure are described. The catalyst systems gave syndio‐rich poly(methyl methacrylate). The α‐diimine system showed much higher activity than the pyridyl bis(imine) systems under similar polymerization conditions. magnified image