THE photovoltaic effect involves the production of electrons and holes in a semiconductor device under illumination, and their subsequent collection at opposite electrodes. In many inorganic semiconductors, photon absorption produces free electrons and holes directly1. But in molecular semiconductors, absorption creates electroná¤-hole pairs (excitons) which are bound at room temperature2, so that charge collection requires their dissociation. Exciton dissociation is known to be efficient at interfaces between materials with different electron affinities and ionization potentials, where the electron is accepted by the material with larger electron affinity and the hole by the material with lower ionization potential3. A two-layer diode structure can thus be used, in which excitons generated in either layer diffuse towards the interface between the layers. However, the exciton diffusion range is typically at least a factor of 10 smaller than the optical absorption depth, thus limiting the efficiency of charge collection3. Here we show that the interpenetrating network formed from a phase-segregated mixture of two semiconducting polymers provides both the spatially distributed interfaces necessary for efficient charge photo-generation, and the means for separately collecting the electrons and holes. Devices using thin films of these polymer mixtures show promise for large-area photodetectors.