Light stimulation was used to trigger the assembly of nanostructures by directly powering changes at the supramolecular level without incurring net chemical changes at the molecular level. Polyethylene imine, a polybase, was mixed in aqueous solution with sodium 1-naphthol-4-sulfonate, an aromatic alcohol, which, in the electronic excited-state, undergoes a short-lived increase in acidity. Excited-state proton transfers between these components were induced by photoexcitation, which led to the formation of hydrogen bonds in the ground-state. Ionic forces, π-π stacking, and hydrophobic effect provided further stabilization. The photoinduced formation of nanosized aggregates was detected by dynamic light scattering and atomic force microscopy. Absorption and emission spectroscopy were used to rule out photochemical reactions and elucidate the supramolecular arrangement.