Abstract The development of advanced experimental and theoretical methods for the characterization of excitations in materials enables revisiting established concepts that are sometimes misleadingly transferred from one field to another without the necessary disclaimers. This is precisely the situation that occurs for excitons in organic materials: different states of matter and peculiarities related to their structural arrangements and their environment may substantially alter the nature of the photo-induced excited states compared to inorganic semiconductors for which the concept of an exciton was originally developed. Adopting the examples of tetracene and perfluorotetracene, in this review, we analyze the nature of the excitations in the isolated compounds in solution, in the crystalline materials, and in melt. Using single crystals or films with large crystalline domains enables polarization-resolved optical absorption measurements, and thus the determination of the energy and polarization of different excitons. These experiments are complemented by state-of-the-art first-principles calculations based on density-functional theory and many-body perturbation theory. The employed methodologies offer unprecedented insight into the optical response of the systems, allowing us to clarify the single-particle character of the excitations in isolated molecules and the collective nature of the electron–hole pairs in the aggregated phases. Our results reveal that the turning point between these two scenarios is the quantum-mechanical interactions between the molecules: when their wave-function distributions and the Coulomb interactions among them are explicitly described in the adopted theoretical scheme, the excitonic character of the optical transitions can be captured. Semi-classical models accounting only for electrostatic couplings between the photo-activated molecules and their environment are unable to reproduce these effects. The outcomes of this work offer a deeper understanding of excitations in organic semiconductors from both theoretical and experimental perspectives.