The radical 1,5-chloropentafluorosulfanylation of vinyl cyclopropanes (VCPs) initiated by Et 3 B/O 2 affords allylic pentafluorosulfanyl/homoallylic chloride products through the ring-strain release of the cyclopropane. The VCP substitution pattern was investigated. The utility of this reaction was illustrated in post-transformation of the C=C bond by ozonolysis, giving access to valuable α-SF 5 carbonyl compounds. Scheme 2. Scope I of the Pentafluorosulfanylation of VCPs: Vinyl Substituent Effect a,b a See Experimental Section for detailed procedures. b Z/E ratios were determined on crude reaction mixtures. c Two equivalents of SF 5 Cl were required to reach full conversion.