The simultaneous control of the tacticity and molecular weight of poly( vinyl acetate) during the radical polymerization of vinyl acetate (VAc) is reported for the first time. A series of fluoroalcohols [(CF3)(3)COH, (CF3)(2)CHOH, PhC(CF3)(2)OH, m-C6H4 {C(CF3)(2)OH}(2)] were employed as solvents for the iodine transfer radical polymerization of VAc, in which the molecular weight of the resultant polymer was determined by the monomer-to-transfer agent ratio and its tacticity was controlled by the solvent. Among the fluoroalcohols, the use of fluorodiol, m-C6H4 {C(CF3)(2)OH}(2), not only led to a higher syndiotacticity (r similar to 60%) but also improved the molecular weight control, resulting in narrow molecular weight distributions (MWD) (M-w/M-n similar to 1.20) in the presence of CH2I(CO2Et) and an azo-initiator [2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile)] at 20 degrees C. High molecular weight polymers (M-n > 7 x 10(4)) with a relatively narrow MWD (M-w/M-n < 1.6) were obtained with the same system. The content of the head-to-head linkages was obviously lower in the fluoroalcohols ( similar to 0.8%) than in the bulk ( similar to 1.2%). Thus, the fluoroalcohols not only led to a higher syndiotacticity but also improved the molecular weight control and the regiospecificity by suppressing the head-to-head propagation.