Phosphonated porphyrin frameworks that are porous to an electron-accepting perylenediimide are systematically interdigitated with a phosphonated form of the diimide to form bulk heterojunctions. When employed in photovoltaics, these molecularly interlaced heterojunctions provide large junction areas while retaining the phase connectivity of traditional bilayer heterojunctions. Zirconium phosphonate linkages facilitate layer-by-layer chromophore assembly from solution under ambient conditions. The dependence of photovoltaic performance on heterojunction architecture is investigated. (c) 2006 The Electrochemical Society.