Porphyrin derivatives are promising materials for various thin-film-based devices such as solar cells, field-effect transistors, and gas sensors. Since the molecular aggregation structure in a thin film significantly influences the device performance, controlling the aggregation structure is of crucial importance. In this study, we show that three different crystalline polymorphs of free-base tetraphenylporphyrin (H2TPP) can be made to form in spin-coated thin films depending on the evaporation time of the solvent. The results show that the aggregation structure in the as-spun films is controlled by the solvent evaporation time, and the initial film structure determines the polymorphs obtained after thermal annealing.