Light-driven changes in supramolecular interactions in perylene bisimides (PBIs) with pendant sulfur-containing functional groups at the bay position are demonstrated. In the ground state, a noncovalent S···X interaction between the σ-hole on sulfur and a heteroatom, X (X = O, N, S), of a neighboring molecule is the main driving force for intermolecular interactions, while in the excited state it is the π-π interaction between PBI scaffolds which drives assembly. The presence of heteroatoms in the solvent results in acceleration of the π-stacking process via the formation of a PBI-solvent complex. The excited-state dynamics involved in the assembly process were revealed via time-resolved fluorescence and transient absorption spectroscopies, while steady-state spectroscopy was used to evaluate the structure of the supramolecular assembly.