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Molecular recognition^{, , –} and supramolecular assembly^{, , –} cover a broad spectrum^{, –} of non-covalently orchestrated phenomena between molecules. Catalysis of such processes, however, unlike that for the formation of covalent bonds, is limited to approaches^{, , –} that rely on sophisticated catalyst design. Here we establish a simple and versatile strategy to facilitate molecular recognition by extending electron catalysis, which is widely applied^{, , –} in synthetic covalent chemistry, into the realm of supramolecular non-covalent chemistry. As a proof of principle, we show that the formation of a trisradical complex between a macrocyclic host and a dumbbell-shaped guest—a molecular recognition process that is kinetically forbidden under ambient conditions—can be accelerated substantially on the addition of catalytic amounts of a chemical electron source. It is, therefore, electrochemically possible to control the …