This paper describes the fabrication of a nanostructured heterojunction of two conjugated polymers by a three-step process: i) spin-coating a multilayered film of the two polymers, ii) rolling the film into a cylinder (a “jelly roll”) and iii) sectioning the film perpendicular to the axis of the roll with an ultramicrotome (nanoskiving). The conjugated polymers are poly(benzimidazobenzophenanthroline ladder) (BBL, n-type) and poly(2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV, p-type). The procedure produces sections with an interdigitated junction of the two polymers. The spacing between the phases is determined by spin-coating (∼15 nm to 100 nm) and the thickness of each section is determined by the ultramicrotome (100 to 1000 nm). The minimum width of the MEH-PPV layers accessible with this technique (∼15 nm) is close to reported exciton diffusion lengths for the polymer. When placed in a junction between two electrodes with asymmetric work functions (tin-doped indium oxide (ITO) coated with poly(3,4-ethylenedioxythiophene:poly(styrenesulfonate) (PEDOT:PSS), and eutectic gallium-indium, EGaIn) the heterostructures exhibit a photovoltaic response under white light, although the efficiency of conversion of optical to electrical energy is low. Selective excitation of BBL with red light confirms that the photovoltaic effect is the result of photoinduced charge transfer between BBL and MEH-PPV.