An ingenious photocatalytic protocol proceeding through sequential functional group migration, radical-polar crossover and stereoconvergent alkene isomerization has been exploited for the radical difunctionalization of unactivated alkynes. A hydroxyalkyl and a (hetero)aryl group can be incorporated into alkynes by this reaction, which stereoselectively furnishes densely functionalized E-allyl alcohols. The method can be applied to the modification of complex structures derived from natural products and drug molecules. Comprehensive experimental studies have been conducted to probe the reaction mechanism, and DFT calculations were carried out to rationalize the selectivity of functional group migration beyond an alkenyl radical-mediated 1,5-HAT. The protocol features broad substrate scope and high product diversity, thus opening up a new prospect for free radical-mediated difunctionalization of unactivated alkynes.