A directing-group-free copper-catalyzed difluoroalkylative benzylation of alkenes with difluoroalkyl bromides and benzylzinc pivalates has been disclosed, thus providing a straightforward access to structurally diverse 1,2-diarylalkanes via 2-fold Csp3-Csp3/Csp3-Csp3 bond formation in a regioselective fashion. Moreover, late-stage modifications of various pharmaceutically active molecules should demonstrate the potential utilizations of this method in medicinal chemistry.