Controlling polymorphism in molecular solids is of great interest since the properties and performances of molecular materials depend on the molecules' mutual packing arrangements. Herein, we describe a perylene bisimide (PBI) organogelator molecule PBI-4 that self-assembles into three different one-dimensional supramolecular polymorphs (Agg 1-3) in the same solvent and at the same concentration at room temperature. The three supramolecular polymorphs were characterized by UV/vis, CD, fluorescence and IR spectroscopy, atomic force microscopy (AFM), and theoretical calculations, revealing that their packing arrangements are governed by distinct π-π-stacking modes and unique hydrogen-bonding patterns. Nudged elastic band (NEB) calculations for the nucleation processes toward Agg 2 and Agg 3 indicate that nucleation starts from a central kinetically trapped state Agg 1 and involves the reorganization of Agg 1 dimers. Time-, concentration-, and temperature-dependent UV/vis experiments provided insights into the thermodynamic stability of the supramolecular polymorphs of PBI-4 and the kinetics for their interconversion. On the basis of this information the production of a certain polymorph could be accomplished either physically by ultrasonication or chemically by seeding. This work contributes to the understanding of polymorphism at the lowest level of hierarchy that is the generation of self-assembled 1D aggregate structures.