The highly enantioselective synthesis of helically chiral 1,1'-bitriphenylenes has been achieved via rhodium-catalyzed double [2+2+2] cycloaddn. of biaryl-linked tetraynes with 1,4-diynes (up to 93% ee). Crystal structures and photophys. properties of these helically chiral 1,1'-bitriphenylenes have also been studied. [on SciFinder(R)]