In this doctoral thesis we present the fabrication and characterization of organic photovoltaic devices (OPVs) assembled onto graphene electrodes and flexible hybrid polymers-based substrates coated with a conductive thin film. For this, initially the graphene films were synthesized by chemical vapor deposition (CVD) technique, followed by modifications in the transfer process of the graphene to the desired substrate. In this step, we developed a new methodology using an EPDM-PAni conductive blend that simplifies the transfer process and improves the electric properties of graphene. We also used another approach which consists in optimizing different hybrid substrates based on PVC, PVA and bacterial cellulose (BC) polymers coated with an ITO conductive thin film. The flexible hybrid substrates as well as the graphene films were investigated by optical transmittance and sheet resistance in order to evaluate their potential use for OPVs applications. Finally, we fabricate various structures of OPVs, using graphene as a conducting electrode, well as using flexible hybrid substrates. Such devices were characterized mainly through their dark and light J×V characteristic curves. In addition, we performed flexion/extension cycles in some devices in order to evaluate their behavior against the mechanical stresses submitted to them. The results showed that the graphene films are a promising material for the application as a transparent conductive electrode in OPVs and the hybrid substrates investigated can be used in flexible devices, since they presented similar behavior to the commonly used inorganic substrates.