The controlled/living radical polymerization of Vinyl acetate (VAc) and its copolymerization with methyl acrylate (MA) were investigated in bulk or fluoroalcohols using manganese complex [Mn-2(CO)(10)] in conjunction with an alkyl iodide (R-I) as an initiator under weak visible light. The manganese complex induced the controlled/living radical polymerization of VAc even in the fluoroalcohols without any loss of activity. The R-I/Mn-2(CO)(10) system was also effective for the copolymerization of MA and VAc, in which MA was consumed faster than VAc, and then the remaining VAc was continuously and quantitatively consumed after the complete consumption of MA. The H-1 and C-13 NMR analyses revealed that the obtained products are block copolymers consisting of gradient MA/VAc segments, in which the VAc content gradually increases, and homopoly(VAc). The use of fluoroalcohols as solvents increased the copolymerization rate, controllability of the molecular weights, and copolymerizability of VAc. The saponification of the VAc units in poly(MA-grad-VAc)-block-poly(VAc) resulted in the corresponding poly(MA-co-gamma-lactone)-block-poly(vinyl alcohol) due to the intramolecular cyclization between the hydroxyl and neighboring carboxyl groups in the gradient segments. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polyrn Chem 47: 1343-1353, 2009