A catalytic defluorinative boroarylation of alkenes with polyfluoroarenes and B2pin2 with the assistance of a PCy3-ligated copper catalyst was developed. Taking advantage of bench-stable alkenes as latent nucleophiles and avoiding traditional reliance on stoichiometric quantities of organometallics, this method showcased good functional group compatibility and proceeded under very mild reaction conditions. A series of valuable boronate-containing polyfluoroarenes including all-carbon quaternary carboncenter-containing triaryl alkylboronates that are otherwise difficult to access were efficiently prepared.