Abstract The reactivity and selectivity of benzene-chlorine atom π-complexes for hydrogen atom abstraction from various alcohols were investigated. Benzene-chlorine atom π-complexes were produced in liquid carbon tetrachloride using the technique of pulse radiolysis at room temperature. The effect of the concentration of benzene and absorbed doses on the formation and decay kinetics were examined and the equilibrium constant of the complex formation was estimated by computer simulation to be 1700 dm 3 mol −1. The absolute rate constants of the reaction of the π-complexes with various alcohols were measured. Partial reactivities for hydrogen abstraction were estimated based on the observed rate constants. The experimental rate contants could be explained as a sum of the partial reactivities of various types of CH bonds. While the hydrogen abstraction rate constants were one order less than those of free chlorine atoms, higher tertiary/primary selectivities were observed for benzene-chlorine atom π-complexes.