A series of air-stable, late transition, metal-based initiators with the structures ML2(C equivalent to CR)(2) (M = Pd and Ni; L = PPh3 and Pn-Bu-3; R = Ph and CH2OH) for the polymerization of (dimethylamino)ethyl methylate (DMAEMA) were developed. Transition metal, phosphine, alkynyl, as well as solvents exhibited significant influence on the polymerization. Among them, Pd(C equivalent to CPh)(2)(PPh3)(2) (PPP) shows the highest activity in CHCl3 for DMAEMA polymerization. The PDMAEMA obtained is a syndiotactic polymer with high number-average molecular weight (M-n) of 20.2 X 10(4). A free radical polymerization mechanism with some ATRP characteristics was proposed for the present polymerization.