We describe how small-molecule ditopic receptors act as catalysts to direct intermolecular [2+2] photodimerizations in the solid state. Examples demonstrate successful applications of mechanochemistry to perform supramolecular catalysis in a solvent-free environment. The approach relies on the process of cocrystallization of multiple components that lead to functional supramolecular structures. We also show how the method can be extended to molecular and supramolecular cascades.