jabbrv-ltwa-all.ldf jabbrv-ltwa-en.ldf The chiral 2,3-dihydrobenzofuran (DHB) scaffold is a privileged motif in bioactive natural products and preclinical therapeutic candidates, yet practical enantioselective syntheses remain scarce. We report a chiral Rh/Hf/(S)-DTBM-SEGPHOS bimetallic catalytic system enabling asymmetric hydrogenation of benzofurans with hydrogen source, delivering diverse DHBs (37 examples) in excellent yields (up to 98%) and enantioselectivities (up to 99% ee). Gram-scale synthesis and deuterium labeling with D 2O (8 examples) validate the method’s scalability and utility in biological studies and drug design.