A metal-free α-alkylation of alcohols with para-quinone methides (p-QMs) for accessing alcohol-containing phenols and dihydroisocoumarins has been developed. The alcohols were converted to α-oxy radicals in the presence of di-tert-butyl peroxide (DTBP), which were added to p-QMs for aromatization and C(sp3)-C(sp3) bond formation.