Chiral polyfluoroarene derivatives are an important scaffold in chemistry. An unprecedented enantioselective C-H alkylation of polyfluoroarenes with alkenes is described. The reaction employs bulky chiral N-heterocyclic carbene (NHC) ligands for nickel catalysts to enable exclusive activation of C-H bonds over C-F bonds and complete endo-selective C-H annulation and excellent enantioselectivity. A wide variety of chiral fluorotetralins, compounds otherwise difficultly accessed but serve as important bioisosteric analogs of both tetralin and heterocycle units for drug design, are expediently synthesized from easily available substrates. To our knowledge, this is the first example of catalytic enantioselective C-H functionalization of polyfluoroarenes.