The first catalytic enantioselective synthesis of planar-chiral dithiaparacyclophanes, e.g., I, by means of cationic rhodium(I)/(S)-BINAPHANE complex-catalyzed reactions of dithiols and 1,4-bis(bromomethyl)benzenes is disclosed. The present method represents the first example of asym. synthesis of planar-chiral cyclophanes through catalytic enantioselective construction of the ansa chains. [on SciFinder(R)]