Allyl sulfides are important organosulfur compounds. K₂S₂O₈ promoted dehydrative cross-coupling between α,α-disubstituted allylic alcohols and thiophenols/thiols is demonstrated for the first time, which resulted in a wide range of allyl sulfides in good to high yields. Note that this metal-free synthetic method features broad substrate scopes; in addition to thiophenols and thiols, pyrazole, sodium benzenesulfinate, and sodium trifluoromethanesulfinate were also tolerated. Mechanistic studies revealed that a radical addition process might be involved in the reaction.