To tailor the nanomorphology in polymer/fullerene blends, we study the effect of electrostatic field (E-field) on the solidification of poly(3-hexylthiophene-2, 5-diyl) (P3HT):[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) bulk heterojunction (BHJ). In addition to control; wet P3HT:PCBM thin films were exposed to E-field of Van de Graaff (VDG) generator at three different directions-horizontal (H), tilted (T), and vertical (V)-relative to the plane of the substrate. Surface and bulk characterizations of the field-treated BHJs affirmed that fullerene molecules can easily penetrate the spaghetti-like P3HT and move up and down following the E-field. Using E-field treatment, we achieved favorable morphologies with efficient charge separation, transport, and collection. We improve; (1) the hole mobility values up to 19.4 × 10 ± 1.6 × 10 cm V s and (2) the power conversion efficiency (PCE) of conventional and inverted OPVs up to 2.58 ± 0.02% and 4.1 ± 0.40%, respectively. This E-field approach can serve as a new morphology-tuning technique, which is generally applicable to other polymer-fullerene systems.