Meet at the border: Assembly of the water-soluble cobalt tetrakis(N-methylpyridinium-4-yl)porphyrin [CoTMPyP]4+ at soft interfaces is enhanced and stabilized by its interfacial interaction with the lipophilic anion (C6F5)4B−. The supramolecular structure thus formed (see picture) provides excellent catalytic activity in the four-electron reduction of oxygen.