In this study, kinetic and mechanism of autocatalytic esterification of citronellol using microwave technique was investigated. Effects of acyl donor type, reaction temperature, molar ratio of citronellol to acetic anhydride, and microwave power level on reaction conversion, yield, and selectivity were investigated. Also, autocatalytic esterification of citronellol using microwave technique was compared to those of chemical and enzymatic esterification. By increasing microwave temperature from 313 to 333 K, the reaction conversion was increased from 53.39% to 94.84%. Also, by increasing the citronellol:acetic anhydride molar ratio from 1:1.5 to 1:4.5, the reaction conversion was increased from 78.88% to 94.84%. Chemical and enzymatic catalysts had no significant effect on improving the reaction conversion when acetic anhydride was used as acyl donor. Based on the modeling studies, it can be concluded that the reaction obeys second-order kinetic model. Microwave technique decreased the activation energy by 2.46% compared to magnetic stirrer technique. In microwave technique, frequency factor and entropy were 4.55- and 1.12-folds higher than those of magnetic stirrer technique, respectively. In conclusion, autocatalytic synthesis of citronellyl acetate using microwave radiation is a simple, low-cost, and safe technique which can be propose to apply instead of conventional chemical and enzymatic methods.