Enantioselective functionalizations of unbiased methylene C(sp3)−H bonds of linear systems by metal insertion are intrinsically challenging and remain a largely unsolved problem. Herein, we report a palladium(II)‐catalyzed enantioselective arylation of unbiased methylene β‐C(sp3)−H bonds enabled by the combination of a strongly coordinating bidentate PIP auxiliary with a monodentate chiral phosphoric acid (CPA). The synergistic effect between the PIP auxiliary and the non‐C2‐symmetric CPA is crucial for effective stereocontrol. A broad range of aliphatic carboxylic acids and aryl bromides can be used, providing β‐arylated aliphatic carboxylic acid derivatives in high yields (up to 96 %) with good enantioselectivities (up to 95:5 e.r.). Notably, this reaction also represents the first palladium(II)‐catalyzed enantioselective C−H activation with less reactive and cost‐effective aryl bromides as the arylating reagents. Mechanistic studies suggest that a single CPA is involved in the stereodetermining C−H palladation step. Crucial combination: A palladium(II)‐catalyzed enantioselective arylation of unbiased methylene β‐C(sp3)−H bonds is enabled by the combination of a strongly coordinating bidentate PIP auxiliary and monodentate chiral phosphoric acids. The synergistic effect between the PIP auxiliary and a non‐C2‐symmetric chiral phosphoric acid is crucial for effective stereocontrol.