We describe detailed studies of ionically self-assembled monolayer (ISAM) photovoltaic (PV) devices incorporating various electron acceptor materials, such as fullerenes and phthalocyanines. Excitons are generated when the conducting polymer is irradiated, and the electron acceptors aid in dissociating the electron/hole pairs before they can radiatively recombine, thus improving the efficiency of the PV process. The ISAM technique allows the deposition of conducting polymer and electron acceptor materials in alternating layers of nanometer-scale thickness. This ensures that every photoexcited electron-hole pair is in proximity to an electron acceptor, thus minimizing electron-hole recombination and increasing the photocurrent. The individual thickness of each monolayer and the interpenetration of adjacent layers can be precisely controlled through the parameters of the electrolyte solutions. Using the ISAM technique, we have demonstrated that it is possible to create ultrathin films (100 nm) of PV material that have enhanced efficiencies.