Limited by the two mutually exclusive phys-icochemical processes of separation and recombination of photogenerated carriers, achieving photolumines-cence and photocatalysis simultaneously is extremely challenging but essential for ever-growing complex issues and specialized scenarios. Here we proposed a biomimetic isolation-conduction strategy induced by an arene-perfluoroarene (A-P) interaction for enabling photoluminescence and photocatalytic hydrogen evolution reaction (HER) activity in the co-assembly of aromatic monomers and octafluoronapthalene (OFN).Inspired by the isolation-conduction effect of periodic isolation of myelin sheaths on the axons of vertebrate nerve fibers by node of Ranvier, we use OFN as a molecular isolator embedded in the aromatic monomers array to block the singlet-to-triplet pathway, while the enlarged intermolecular dipoles resulting from the A-P interactions facilitate the conduction of photogenerated carriers in the isolated regions. The resultant co-assembly exhibits an enhanced monomeric green emission compared to the corresponding monocomponent self-assembly with weak red emission. Meanwhile, it also has an enhanced photocatalytic HER performance with a rate of 2.45 mmol g^-1h^-1, which is 15.2 times more than the self-assembled one. On this basis, a sequential fluoric wastewater reuse system that includes real-time fluorescence detection/removal of perfluorooc-tanoic acids and photocatalytic HER device is constructed.