The enantioselective synthesis of phenanthrenol-based [9]helicene-like molecules has been achieved via the rhodium-mediated intramolecular [2 + 2 + 2] cycloadditions of 3-phenanthrenol-linked triynes. Crystal structures and photophysical/chiroptical properties of these [9]helicene-like molecules were compared with the corresponding [7]helicene-like molecules.