highly desirable but has not been achieved. Radical rearrangement has been shown to be a pre-eminent synthetic tactic for the transformation of unsaturated carbon-carbon bonds 29-34 , and may support difunctionalization of unactivated alkynes. Taking advantage of radical rearrangement we report a proof-of-concept study, in which aliphatic alkynes can be transformed stereoselectively into valuable multisubstituted E-allyl alcohols . This photoredox neutral cascade proceeds through sequential radical migration, radicalpolar crossover and energy transfer (ET)-promoted stereoconvergent alkene isomerization. DFT calculations have been carried out to rationalize the unique selectivity of functional group migration beyond the alkenyl radical-induced 1,5-HAT that probably occurs with aliphatic alkynes.