Since fullerenes are available in macroscopic quantities from fullerene soot, large efforts have been geared toward designing efficient strategies to obtain highly pure fullerenes, which can be subsequently applied in multiple research fields. Here we present a supramolecular nanocage synthesized by metal-directed self-assembly, which encapsulates fullerenes of different sizes. Direct experimental evidence is provided for the 1:1 encapsulation of C60, C70, C76, C78 and C84, and solid state structures for the host–guest adducts with C60 and C70 have been obtained using X-ray synchrotron radiation. Furthermore, we design a washingbased strategy to exclusively extract pure C60 from a solid sample of cage charged with a mixture of fullerenes. These results showcase an attractive methodology to selectively extract C60 from fullerene mixtures, providing a platform to design tuned cages for selective extraction of higher fullerenes. The solid-phase fullerene encapsulation and liberation represent a twist in host–guest chemistry for molecular nanocage structures. ; This work was supported by grants from the European Research Council (Starting Grant Projects ERC-2011-StG-277801 and ERC-2009-StG-239910), the Spanish MICINN (CTQ2012-37420-C02-01/BQU, CTQ2012-32436, CTQ2011-23156/BQU, CTQ2011-25086/BQU, Consolider-Ingenio CSD2010-00065, INNPLANTA project INP-2011-0059-PCT-420000-ACT1, MAT2012-30994, a RyC contract to I.I., a JdC contract JCI-2012-14438 and CIG (FP7-PEOPLE-2013-CIG-630978) to S.O. and a PhD grant AP2010-2517 to M.G.B.) and the Generalitat de Catalunya (2009SGR637 and a PhD grant to C.G.S.). ; Peer Reviewed