The reaction of 1-octene with the lead tetraacetate–hydrogen fluoride reagent led to products resulting from the Markovnikov addition of lead and its ligand (fluoro or acetoxy) to the olefinic double bond. Displacement of lead from the organometalic intermediate via three separate pathways could be distinguished; displacement concomitant with hydride migration alkyl migration, or direct displacement by an external ligand. The pathways for the formation of the product difluorides, fluoroacetates, and diacetate could be followed by an analysis of the products obtained from carrying out the reaction using 1-octene-1-13C as substrate. The major pathways to product formation resulting from either hydride or alkyl migration could be rationalized as proceeding through the intermediacy of a resonance stabilized α-fluorocarbonium ion.