A copper-catalyzed regiodivergent chloropentafluorosulfanylation strategy for 1,3-enynes using SF5Cl has been developed. The regioselectivity is dictated by the structural and substitution patterns of 1,3-enynes, enabling facile access to three classes of SF5-containing products: propargylic chlorides, 1,3-dienes, and allenes. The reaction systems involve radical species, where the transfer of a chlorine atom from SF5Cl to a carbon radical is considered the predominant pathway. Diverse types of SF5- building blocks can be synthesized through simple functional group transformations.