Because of favorable charge transport properties with a lower possibility of recombination, bilayer structure solar cells have received significant ongoing attention. The simplest approach to obtain better transport properties of a charge carrier is to increase the crystallinity of the active layer. In this work, we investigated the effect of the crystallinity of poly(3-hexylthiophene) (P3HT) on the PCE of bilayer solar cells. The self-assembled nano-fibril morphology induced by the addition of the non-soluble acetonitrile (AN) solvent induces a significant improvement of charge transport properties in field-effect transistors (FET). However, the self-assembled nano-fibril morphology of P3HT did not have a beneficial effect on the bilayer solar cells. Since the P3HT nano-fibrils were generally placed in parallel with the substrate, the FET device which uses lateral transport could produce an enhancement of the device properties. However, because of the difficulty of charge transport in the vertical direction between horizontally aligned fibrils, the properties of the solar cell device did not improve with increased P3HT crystallinity. Therefore, we concluded that simply increasing the crystallinity may not be sufficient to deliver a PCE enhancement in bilayer structures because of the anisotropic transport properties of the semiconducting polymer which depend on the orientation of the backbone. (C) 2014 Elsevier B. V. All rights reserved.