The design and development of new polymeric functional material for application in organic optoelectronic devices, like polymer solar cells, is one of the most active areas of research, mainly due to the continuous search for low cost renewable energy sources. Flexibility, solution processability, and short energy payback time, are among the very important characteristics of the organic based materials that make possible their application in large area devices. However, despite the facts that high power conversion efficiencies have been attained with bulk heterojunction structures, and that the potentiality of the organic photovoltaic technology is still huge, to date industrial production and large scale commercialization have not been achieved, a major issue being the transfer of the efficiencies obtained on small area cells to large area modules. Thus, the development of new polymeric materials and devices construction methods are still necessary, in order to find procedures that allow the implementation of this relevant technology.

            One of the principal difficulties that the use of organic polymers in electronics has to face is the film deposition methodology over the conducting or semiconducting contacts. The most common approaches rely on thermal evaporation and solution-processing methods. However, thermal evaporation requires materials with adequate sublimation capability and thermal stability, properties that are difficult to reach in polymers. Also, solution processes, such as dip - or spin - coating methodologies, require polymeric materials with intrinsic high solubility. On the contrary, electropolymerization of suitable photoelectroactive monomers allows the synthesis and formation of polymeric films in one step, with the possibility to get control over pattern and thickness, two very important aspects in the implantation of industrial processes. In the last years we developed porphyrin polymeric materials, produced by electrochemical methods. These materials exhibited photovoltaic and electrochromic properties. The monomers were planned with the aim to achieve their polymerization through dimerization of the electrochemically generated tryphenyl amine and/or carbazole radical cations, giving rise to tetraphenylbenzidine and/or dicarbazole substructures with hole transport capability. These polymers demonstrate their capacity for the generation of photoinduced charge separated states, with light absorption in a broad region of the visible spectrum, and hold the potentiality for their application in the development of optoelectronic devices.