have served as prototypes for the meticulous design of supramolecular catalysts. [2] In recent years, many efforts have been devoted to developing abiotic systems able to mimic such catalytic proficiencies by means of host-guest supramolecular interactions. [3] However, finding highly active supramolecular catalytic systems is not a trivial task. In enzymes, their tertiary structure defines a shielded catalytic pocket, allowing strong noncovalent forces even in highly competitive environments (i.e., water). [4] On the contrary, for an abiotic supramolecular catalytic system, the host-guest interactions (i.e., hydrogen bonding, halogen bonding, π-π-stacking, dipolar aggregation, and solvophobic forces) that define the supramolecular microenvironment facilitating an active and selective transformation are usually very sensitive to the nature of the solvents. [5] Thus, it is important that solvent effects are taken into account when designing new supramolecular catalytic systems. Very often, the behavior of such systems is enhanced using noncompetitive organic solvents, which can be highly toxic and/or display high boiling points (toluene, dimethyl sulfoxide, etc.), and under relatively dilute conditions, leading to an increased usage of solvents. This results in both waste generation and an increased energy demand for the separation steps, often overpassing the one involved in the targeted chemical transformation. A promising solution to overcome these issues is the use of solid solvents. These systems are organic/inorganic materials that provide a solvent-like solid medium, onto which host molecules can be grafted in a controlled manner defining, at the molecular scale, the microenvironment required to favor the host-guest supramolecular interactions. Although some bioinspired solid solvents have shown promising results on this behalf, this is still a seldom explored field. [6] The growing emissions of carbon dioxide to the atmosphere have triggered the blossoming of technologies for its capture, activation, and conversion into added value chemicals. [7,8] Nevertheless, the high kinetic and thermal stability of CO 2 appears as a major challenge. [9] Hence, the development of new catalysts for CO 2 transformation, able to work at mild process conditions with good performance, and being also reusable and easily separable, is of high industrial interest. [10,11] Among the different added-value products that have been obtained using carbon dioxide, [12][13][14] cyclic Supramolecular catalysis can provide distinct advantages for the catalytic conversion of CO 2 into carbonates by cycloaddition to epoxides. For example, the absence of metals in the catalytic site, and the easy design for optimization. The incorporation of multiple functionalities in pseudopeptidic macrocycles with a pendant arm allows catalytic systems to be obtained where halide anions (nucleophilic activating agents for epoxides), hydrogen bond acceptor sites (activating agents for epoxides and stabilizing sites for anionic intermediates), and amine g...