Homogeneous catalysis is witnessing a radical change in perspective, with an increasing awareness that a clear understanding of the nanometric tridimensional space where the reactions take place plays a key role in controlling both the activity and even more importantly the different selectivities of chemical transformations. The understanding of what happens at this level during a catalytic process can spur further achievements in deciphering biological phenomena such as enzyme activity. Supramolecular interactions are currently considered in homogeneous catalytic reactions, and a better definition of the nano‐space around the active site is the target for developing more active and selective systems.