Diphenyl(2,6-dimesitylphenylthio)bismuthine (1a) serves as an excellent cocatalyst in organo-bismuthine-mediated living radical polymerization (BIRP). Both low and high molecular weight polystyrenes and poly(butyl acrylate)s (PBAs) with controlled molecular weights and low polydispersity indexes (PDIs) were synthesized by the addition of a catalytic amount of 1 a to an organobismuthine chain-transfer agent, methyl 2-dimethylbismuthanyl-2-methylpropionate (3). The number-average molecular weight (M,,) of the resulting polymers increases linearly with the monomer/3 ratio. Structurally well-defined polystyrenes with M-n's in the range from 1.0 x 10(4) to 2.0 x 10(5) and PDIs of 1.07-1.15 as well as PBAs with M-n's in the range from 1.2 x 10(4) to 2.8 x 10(6) and PDIs of 1.06-1.43 were successfully prepared under mild thermal conditions. Control experiments suggested that 1 a reversibly reacts with the polymer-end radical to generate an organobismuthine dormant species and 2,6-dimesitylphenylthiyl radical (2a). This reaction avoids the occurrence of chain termination reactions involving the polymer-end radicals and avoids undesired loss of the bismuthanyl polymer end group. The bulky 2,6-dimesitylphenyl group attached to the sulfur atom may prevent the addition of thiyl radicals to the vinyl monomers to generate new polymer chains.