An efficient free-radical-promoted unactivated C(sp3)-H dehydrogenative coupling reaction of free alcohols at the δ position with quinone and chromone has been developed. This reaction has a good functional group tolerance and substrate scope; various alcohols reacted with quinones and chromones to give the corresponding C(sp2)-H alkylation products in moderate to good yields. A gram-scale experiment can be successfully operated. This protocol provides a sustainable and practical strategy for the late-stage functionalization of alcohols with quinones and chromones by constructing the challenging δ-selective C(sp3)-C(sp2) bond.