A modular approach for the synthesis of polymer networks with well-defined node and cross-linking dimensions is described. Each node or tie point in the network is a cyclodextrin molecule, which imparts discrete molecular guest–host capabilities to the network. C60 fullerenes homogeneously intercalate in the network, presumably via van der Waals guest–host interactions with the hydrophobic γ-cyclodextrin cavity, resulting in stable C60-filled polymer networks with improved mechanical properties. Networks prepared with α-cyclodextrin, whose inner cavity is smaller than γ-cyclodextrin, and smaller than the C60 diameter, do not yield materials with stable C60 intercalation. Characterization of the final composites reveals that the cross-linked γ-cyclodextrin-based composites maintain stable C60 concentrations, even after multiple extractions with toluene, which itself is a good solvent for C60. Membranes prepared from the cyclodextrin polymer network, prior to C60 intercalation, should also be useful for C60 extraction from C60–solvent mixtures. The synthetic route we describe here is not limited to C60 and should be generally applicable to a wide variety of guests.