Palladium-catalyzed asymmetric functionalization of unbiased methylene C(sp³)–H bonds is a long-standing challenge. Here, we report a Pd(II)-catalyzed highly enantioselective arylation of unbiased methylene C(sp³)–H bonds enabled by a strongly coordinating bidentate 2-pyridinylisopropyl (PIP) directing group and an easily accessible 3,3′-F₂-BINOL chiral ligand. The use of aryl iodides with the combination of 3,3′-F₂-BINOL was beneficial for high enantiocontrol. A range of aliphatic amides and aryl iodides were tolerated, providing the desired arylated products in high enantioselectivities (up to 96% ee). The PIP directing group could be removed under mild conditions without erosion of enantiopurity.