Polymer photovoltaic devices commonly suffer from low power conversion efficiencies despite the potential for much higher performance. Here we apply a recently reported system for creating a chemically fixed polymer p-i-n junction to polymer photovoltaic devices. Both single-component and blended donor/acceptor devices are fabricated and tested. We study the devices during charging and find that the changes in light and dark current characteristics are consistent with the formation of a p-i-n junction in the active material. While the overall performance of these systems need improvement, the devices show promising open circuit voltages, suggesting the possibility for improving the state-of-the-art in polymer photovoltaic technologies with continued materials development.