A practical general method for asymmetric intermolecular benzylic C(sp3)−H amination has been developed by combining the pentafluorobenzyl sulfamate PfbsNH2 with the chiral rhodium(II) catalyst Rh2(S‐tfptad)4. Various substrates can be used as limiting components and converted to benzylic amines with excellent yields and high levels of enantioselectivity. Additional key features for the reaction are the low catalyst loading and the ability to remove the Pfbs group under mild conditions to give NH‐free benzylic amines.