A route to enantiopure (O-methyl)6-2,6-helic[6]arenes (+)-P-2and (−)-M-2has been provided. By the reaction of enantiopure triptycene precursors (+)-1and (−)-1in refluxed o-DCB for 12 h in the presence of catalytic amount of FeCl3, and then followed by treatment of the obtained oligomers under the same conditions, (+)-P-2and (−)-M-2could be obtained in 51% and 53% total yield, respectively. It was also found that racemic and enantiopure (O-methyl)6-2,6-helic[6]arenes could be easily brominated by Br2to give the corresponding hexabromo-substituted helic[6]arene derivatives rac-4, (+)-P-4, and (−)-M-4in high yields. The crystal structure of (+)-P-4further confirmed the absolute configuration of the helic[6]arenes and their derivatives. Moreover, a series of hexaaryl-substituted helic[6]arene derivatives 5a–fwith deepened cavities could be conveniently synthesized in 55–71% yield by Suzuki–Miyaura coupling reactions of 4and arylboronic acids. rac-5acould encapsulate chloroform and exhibit self-sorting stacking in solid state. Enantiopure (+)-P-5a–fand (−)-M-5a–fshowed mirror images in their CD spectra.