Herein, we disclose a unique directing effect of 9-substituted triptycenes in electrophilic substitution to achieve the regioselective functionalization of the triptycene core. The Hirshfeld population analysis was adopted to predict the selectivity in electrophilic substitution. TMS and t-Bu groups were found to considerably accelerate the reaction at C2 positions to produce C3-symmetric isomers. Correlation between distortion and charge distribution within benzene rings was systematically examined.