Homogenous polymerization of methyl methacrylate using Pd(II)-and Ni(II)-based acetylide complexes as initiators has been investigated. M(PR3')(2)(C=CR)(2) (M = Pd, Ni; R'- PPh3, Pn-Bu-3; R - Ph, CH2OH, CH2OOCCH3, CH2OOCPh, CH2OOCPhOH-o) were found to be a novel type of effective initiators for the polymerization of methyl methacrylate. Among them, Pd(C=CPh)(2)(PPh3)(2) (PPP) shows the highest activity in the MMA polymerization and the PMMA obtained is a syndiotactic polymer with high number-average molecular weight (M-n) of 14.1 x 10(4). Some features and kinetic behavior of MMA polymerization initiated by PPP were studied in detail. The polymerization reaction is first-order with respect to both [PPP] and [MMA]. Radical polymerization mechanism is proposed.