New methods connecting molecular structure, self-organization, and optoelectronic performance are important for understanding the current generation of organic photovoltaic (OPV) materials. In high power conversion efficiency (PCE) OPVs, light-harvesting small-molecules or polymers are typically blended with fullerene derivatives and deposited in thin films, forming a bulk heterojunction (BHJ), a self-assembled three-dimensional nanostructure of electron donors and acceptors that separates and transports charges. Recent data suggest micrometer-scale orientational order of donor domains exists within this complex nanomorphology, but the link to the optoelectronic properties is yet unexplored. Here we introduce polarization-dependent, photoconductive atomic force microscopy (pd-pcAFM) as a combined probe of orientational order and nanoscale optoelectronic properties (∼20 nm resolution). Using the donor 7,7′-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b′]dithiophene-2,6-diyl)bis(6-fluoro-4-(5′-hexyl[2,2′-bithiophen]-5-yl)benzo[c][1,2,5]thiadiazole), p-DTS(FBTTh2)2, we show significant spatial dependence of the nanoscale photocurrent with polarized light in both pristine and BHJ blends (up to 7.0% PCE) due to the local alignment of the molecular transition dipoles. By mapping the polarization dependence of the nanoscale photocurrent, we estimate the molecular orientation and orientational order parameter. Liquid crystalline disclinations are observed in all films, in agreement with complementary electron microscopy experiments, and the order parameter exceeds 0.3. The results demonstrate the utility of pd-pcAFM to investigate the optical/structural anisotropy that exists within a well-performing BHJ system and its relationship to optoelectronic properties on both the nanometer and micrometer length scales.