A di-tert-butyl peroxide (DTBP)-promoted difunctionalization of α-aryl α-alkynyl allylic alcohols with alkyl nitriles was developed, affording a series of α-alkynyl γ-cyano functionalized ketones in moderate yields. This procedure involved C(sp3)-H bond cleavage of alkyl nitriles and radical 3-exo-dig cyclization. After this, radical 1,2-alkynyl migration is preferred rather than 1,2-aryl migration.