The thermo-oxidative behavior and kinetic study of cinnamyl diesters having different aliphatic chain lengths in the structure were studied by the TG/DSC/FTIR coupled method. The degradation processes on the studied esters occurred through several overlapping steps, between 150 and 450 degrees C, linked to different gaseous products emitted and with changes of E(alpha) values as (alpha) increased. The initial stage of cinnamyl diester degradation (for alpha <= 0.15) was independent of the kind and length of the aliphatic chain, and the energetic barrier necessary to break the ester linkages was independent of the transformation degree (ca. 60-80 kJ mol(-1)). A progressive increase in the E(alpha) values from ca. 80 kJ mol(-1) to 200-250 kJ mol(-1) (for 0.15 <= alpha <= 0.40) suggested the existence of competitive reactions which were due to chemical recombination processes in the gas phase, involving oxidation reactions of volatile organic fragments with oxygen. However, as alpha is changed between 0.40 <= alpha <= 0.75, the high data dispersion and the marked increase in experimental error in the E(alpha) values indicated a strong dependence of the kinetic parameters on conversion degree and complexity of chemical processes taking place. Finally, for 0.8 <= alpha the decrease in E(alpha) values suggested modifications of degradation mechanism and indicated that the easy oxygen accessibility toward the sample promotes the fast gasification reaction of the carbonaceous residues. (C) 2015 Elsevier B.V. All rights reserved.