An enantioselective Cu/Pd-catalyzed borylative coupling of styrenes with aryl/alkenyl iodides was realized using a chiral sulfoxide-phosphine (SOP) ligand. Enantioenriched 1,1-diarylethyl and beta-arylhomoallylic boronates are readily prepared. A streamlined procedure merging arylboration and subsequent Pd-catalyzed Suzuki-Miyaura cross-coupling enables the modular assembly of enantioenriched 1,1,2-triarylethanes, including two medicinally important chiral small-molecule targets.