Recently conjugated polymers have been of great interest for their electronic properties that can be easily varied making them very suitable for quite large area of optoelectronic applications, such as electroluminescent diodes and photovoltaic solar cells. Polyazomethines are among these materials as they have nitrogen atoms built in their backbones and interesting properties of this group of materials result from the electron lone pair orbital allocated on the nitrogen atom. Among polyazomethines there are isoelectronic analogues of much better known optoelectronic materials, i.e. polyphenylenevinylene (PPV) and fluorine-based polymers which is very promising from the point of view of potential applications of the materials studied. Based on the Huckel theory of molecular orbitals of conjugated polymers, the electronic structure of thin films of various polyazomethines will be outlined and applied to interpret their absorption and photoluminescence spectra.