<h2>Summary</h2> Asymmetric coupling of 1,3-dienes with carbonyl compounds is one of the most powerful tools for atom-economical construction of the Csp<sup>3</sup>–Csp<sup>3</sup> bond. Although many methods have been established for the coupling of 1,3-dienes, stereodivergent variants remain a formidable challenge because of their innate stereoselective bias (<i>syn</i>- or <i>anti</i>-) in a single catalyst system. Herein, we report a synergistic Pd/Lewis-base-catalyzed stereodivergent coupling of 1,3-dienes with pentafluorophenyl acetates. All four stereoisomers of the coupling products could be selectively obtained from the same pair of substrates simply by varying the relative chirality of the two catalysts. Coupled with the late-stage transformation of the pentafluorophenyl moiety, this method provides a general method to prepare various chiral molecules bearing vicinal stereocenters.