Addition of various polyfluoroalkyl halides including 1,2-dihalopolyfluoroalkanes to1-octene is effected by using a catalytic amount of Cp_2TiCl_2(IV) and iron powder to give 1:1 adductsin excellent yields. The reaction is performed in EtOH or THF. A Cp_2TiCl(Ⅲ) mediatedradical mechanism is proposed. Radical reactivity of polyfluoroalkanes toward 1-octene was foundto be --CF_2I> -CF_2Br >-CF_2CCl_3.