Linalool (LIN) and vinyl acetate (VA) were copolymerized by benzoyl peroxide (BPO) in p-xylene at 60degreesC for 90 min. The system follows nonideal kinetics: R(p)alpha[I](0.6)[LIN](1.2)[VA](1.1). It results in the formation of alternating copolymer as evidenced from reactivity ratios as r(1) (VA) = 0.01, r(2) (LIN) = 0.0015, which have been calculated by Kelen-Tudos method. The overall activation energy is 82 kJ/mol. The FTIR spectrum of the copolymer shows the presence of the band at 3425 cm(-1) due to alcoholic group of LIN and at 1641 cm(-1) due to >C=O group of VA. The H-1-NMR spectrum shows peaks at 7.0-7.7 delta due to hydroxy proton of LIN and at 1.0-1.4 delta due to acetoxy protons of VA. C-13-NMR spectrum of copolymer shows peaks at 167 ppm due to acetoxy group and at 75-77 ppm due to C-OH group. The Alfrey-Price Q-e parameters for LIN has been calculated as Q(2) = 1.24 and e(2) = 3.11. The copolymer is highly thermally stable and has a glass transition temperature (T-g) of 85degreesC, evaluated from DSC studies. The mechanism of copolymerization has been elucidated. This article also reports measurement of Mark-Houwink constants in THF at 25degreesC by means of GPC as alpha = 0.8 and K = 3.0 X 10(-4) dl/g. The thermal decompositions of copolymer are established with the help of TGA technique. (C) 2004 Wiley Periodicals, Inc.