Abstract: In order to study the kinetic rate constants and the discrepancy of reaction activities of O₃ with unsaturated alcohols, we studied the reaction kinetics of 5 kinds of hexen-ols and O₃ in smog chamber using the absolute rate method. The kinetic rate constant of Z-2-hexen-1-ol, E-2-hexen-1-ol, Z-4-hexen-1-ol, E-4-hexen-1-ol, and 5-hexen-1-ol with O₃ at 298 K, 101, 325 Pa was (8.94×10^-17±0.8×10^-17), (13.95×10^-17±0.48×10^-17), (8.82×10^-17±0.31×10^-17), (10.01×10^-17±1.03×10^-17), and (0.82×10^-17±0.04×10^-17)cm³/(molecule·s), respectively. Through the results of theoretical calculations, the different trends of kinetic rate constants were explained. The reaction activity of different hexen-ols with O₃ was efficiently influenced by the position of —OH and double bond. The atmospheric lifetime of hexen-ols was calculated through the kinetic rate constants and the normal concentration of atmospheric oxidants, which indicated the competitive reactions of O₃, OH, and NO₃ radicals in the elimination process of Z-2-hexen-1-ol, E-2-hexen-1-ol, Z-4-hexen-1-ol, and E-4-hexen-1-ol. However, these hexen-ols were mainly eliminated by O₃ in high photochemical pollution areas. The atmospheric lifetime of 5-hexen-1-ol was more than 7 h due to the conformation characteristics. Therefore, O₃ had an obvious impact on the removal of 5 hexen-ols. Our results provide the important kinetic parameters for the air quality prediction simulation of the dynamic models in the human-gathering areas, and provide theoretical support for the determination and prediction of the rate constants of the similar reactions between enols and O₃.