Low-density, solid-state, porous supramolecular organic frameworks are constructed using pillarenes. The frameworks have a honeycomb-like structure, permanent porosity, high thermal stability, and selective and reversible sorption properties toward CO2. The exceptionally selective CO2-sorption properties (375/1, 339/1) of one framework over N2 and CH4 indicate potential applications in CO2-capture for post-combustion power plants and natural gas sweetening. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.