So-called molecular containers or capsules have received a great deal of attention in recent years related to the unique properties and behaviors that arise in systems of intimately associated molecules-within-molecules.  In this context, judicious exo- or endo-functionalization of the molecular cavities will dramatically influence the molecular recognition and/or assembly properties of these important supramolecular hosts.  A variety of exo-funtionalized cryptophane molecular containers will be discussed.  Specifically, the appendage of electron withdrawing transition-metal fragments directly to the exterior faces of cryptophanes results in cationic capsules, such as 1, that selectively encapsulate anionic species.  Further, exo-carboxylic acid derivatized cryptophanes, such as 2, have been synthesized as ligands for novel metal-organic framework (MOF) materials.  It is anticipated that “microcavity-within-micropore” materials derived from molecular containers will display selective sorption and storage properties commensurate with the molecular recognition properties of their building blocks.