The template-assisted fabrication of well-ordered interpenetrating donor/acceptor nanostructures based on polymeric semiconductors on conductive substrates is reported. Arrays of free-standing crosslinked tetraphenylbenzidine based nanorods are fabricated utilizing sacrificial AAO templates. TEM confirms the obtained donor/acceptor nanostructure morphology. The embedded nanorods show no aggregation and collapse of the rods within the film. Photoluminescence measurements reveal a more than three fold improvement in photoluminescence quenching relative to the planar bilayer architecture. The approach offers a versatile all-solution-based technique for the fabrication of well-ordered bulk heterojunction films with a large donor/acceptor interface for the application in polymer/polymer photovoltaic devices.