Promoting a drug inclusion proportion in hydrophobic cavity of β-cyclodextrin using simple methods is a highly ambitious task. Herein, we report the crowning β-cyclodextrins formed by intramolecular hydrogen bonding interaction, which has greatly prolonged the cavity depth of β-cyclodextrin, and therefore further efficiently improved the inclusion proportion to complex drug molecule (vitamin E). Furthermore, the self-assembly behaviors, controllable release, and antioxidant properties of vitamin E embedded into the cavity of crowning β-cyclodextrins was investigated, and host-guest inclusions exhibited temperature-responsive controlled release, excellent antioxidant activity, and photostability.