It has been established that a chiral S-shaped [11]helicene-like mol. can be synthesized with high ee value along with a meso form by the rhodium(I)/(R)-difluorphos complex-mediated enantioselective intramol. double [2+2+2] cycloaddn. of a 2-naphthol-linked hexayne, even though this chiral helicene has the collision between the terminal benzene rings. Epimerization behavior of the chiral and meso [11]helicene-like mols. have also been disclosed. [on SciFinder(R)]