Herein we describe the first construction of fluorinated tertiary stereocenters based on an alkene C( sp 2 )–C( sp 2 ) bond cleavage. The new process, that takes advantage of a Rh-catalyzed carbyne transfer, relies on a branched-selective fluorination of tertiary allyl cations and is distinguished by a wide scope, late-stage applications and adaptability to radiofluorination.