This paper is focused on thin films of various aromatic polyazomethines, undoped and doped with iodine and FeCl3, which are expected to be promising materials for organic electronics. Polyazomethine thin films have been fabricated by thermal vacuum evaporation (TVE) and chemical vapor deposition (CVD) via the polycondensation process. The prepared films, with a typical thickness of the order of 100 nm and smooth surfaces, appear to be considerably amorphous. The measured absorption and photoluminescence (PL) spectra are discussed in terms of the electronic structure of the materials of interest. In particular, the lowenergy spectra, related to transitions between the delocalized states, reveal the presence of the vibronic progression. Additionally, the influence of the polymer chain structure and its conformation on the electronic structure of polyazomethine thin films is considered. Finally, the relationship between the electronic processes occurring in polyazomethine thin films and their potential applications is discussed.