Poly(vinyl alcohol-co-vinyl levulinate) was synthesized by NN-dicyclohexylcarbodiimide assisted esterification of poly(vinyl alcohol) with free levulinic acid using 4-pyrrolidino pyridine as a catalyst in N,N-dimethyl acetamide/lithium chloride solvent system in order to optimize the reaction condition. The vinyl levulinate content in the copolymer was attained up to 0.95. The C-13 NMR dyad compositional analysis indicated the block character of the copolymer was 0.92, suggesting almost random poly(vinyl alcohol-co-vinyl levulinate) was formed. Glass transition temperature dependence on vinyl levulinate content of the copolymers fitted better into Gordon-Taylor equation as compared with Fox equation and the glass transition temperature of poly(vinyl levulinate) was given as 2.3 degrees C by the least regression method. (c) 2005 Elsevier Ltd. All rights reserved.