Using a short peptide precursor modified by the biaryltetrazole with intramolecular photo-click reactivity, we realized the photo-regulation of the pericellular nanofibers formed by the enzyme-instructed self-assembly on the cell membrane. Upon light irradiation, the fluorescence of nanofibers could be turned on to monitor both enzyme-instructed self-assembly and photo-induced disassembly processes. Moreover, the cell fate could be controlled through the photo-regulation.