Palladium-catalyzed decarbonylative alkylation reactions of acyl fluorides have been developed using alkylboranes having β-hydrogens. A wide range of functional groups were well tolerated, even at the high temperature required for decarbonylation. This protocol provides a diverse C(sp2)-C(sp3) bond formation via a highly efficient decarbonylative process. The hemilabile bidentate ligand DPPE plays a crucial role for retardation of the undesired β-hydride elimination.