Radical polymerization of methyl mcthacrylate (MMA) initiated with various diacyl peroxideamine systems was studied. Benzoyl peroxide (BPO) and lauroyl peroxide (LPO) were used as diacyl peroxide component, N,N-dimethyl aniline (DMA) and its para substituted derivatives, i.e., N,N-dimethyl-p-toluidine (DMT), p-hydroxymethyl-N,N-dimethyl aniline (HDMA), p-nitro-N,N-dimethyl aniline (NDMA) and p-dimethylamino benzaldehyde (DMAB) were used as amine components. It was found that the peroxide-DMT systems give higher rates of bulk polymerization R_p of MMA than the organic hydroperoxide-DMT systems with the following descending order BPO-DMT>LPO-DMT>CHP (cumene hydroperoxide)-DMT>TBH (tert-butyl hydroperoxide)-DMT. The aromatic tertiary amines possess obvious structural effect on the R_p values in the diacyl peroxideamine system. The overall activation energy of MMA polymerization was determined and thekinetics of polymerization of MMA initiated with BPO-DMT system was investigated. Benzoyl peroxide (BPO) and lauroyl peroxide (LPO) were used as diacyl peroxide component, N, N-dimethyl aniline (DMA) and its para substituted derivatives, ie N-dimethyl-p-toluidine (DMT), p-hydroxymethyl-N, N-dimethyl aniline (HDMA), p- nitro- N, N-dimethyl aniline (NDMA) and p- dimethylamino benzaldehyde (DMAB) were used as amine components. It was found that the peroxide-DMT systems give higher rates of bulk polymerization R_p of MMA than the organic hydroperoxide-DMT systems with the following descending order BPO-DMT> LPO-DMT> CHP (cumene hydroperoxide) DMT> TBH (tert-butyl hydroperoxide) -DMT. This aromatic tertiary amines possess obvious structural effect on the R_p values ​​in the diacyl peroxideamine system. The overall activation energy of MMA polymerization was determined and thekinetics of polymerization of MMA initiated with BPO-DMT system was investigated.