Abstract The role of molecular spectroscopy in astrophysics and astrochemistry is discussed in the context of the study of large, complex, carbon-bearing molecules, namely, polycyclic aromatic hydrocarbons (PAHs). These molecular species are now thought to be widespread in the interstellar medium in their neutral and ionized forms. Identifying the carriers responsible for unidentified interstellar spectral bands will allow to derive important information on cosmic elemental abundance as well as information on the physical conditions (density, temperature) reigning in specific interstellar environments. These, in turn, are key elements for a correct understanding of the energetic mechanisms that govern the origin and the evolution of the interstellar medium. A multidisciplinary approach — combining astronomical observations with laboratory simulations and theoretical modeling — is required to address these complex issues. Laboratory spectra of several PAHs, isolated at low temperature in inert gas matrices or seeded in a supersonic jet expansion, are discussed here and compared to the astronomical spectra of reddened, early type, stars. The electronic spectroscopy of PAHs in the ultraviolet, visible and near-infrared domains is reviewed and an assessment of the potential contribution of PAHs to the interstellar extinction in the ultraviolet and in the visible is discussed.