AbstractFabrication of bulk heterojunctions with well-ordered arrays of organic and inorganic semiconductors is a promising route to increasing the efficiency of polymer photovoltaic cells. In such structures, almost all excitons formed are close enough to the organic–inorganic interface to be dissociated by electron transfer, all charge carriers have an uninterrupted pathway to the electrodes, and polymer chains are aligned to increase their charge carrier mobility. Furthermore, ordered structures are interesting because they are relatively easy to model. Studies of ordered cells are likely to lead to better design rules for making efficient photovoltaic cells.