Self-assembled and well-aligned nanowires (NWs) of poly(3-hexylthiophenes) (P3HT) embedded within insulating polystyrene (PS) matrix were found to have a high field-effect carrier mobility. We demonstrate that solution shear coating of P3HT-NWs/PS nanocomposites is an effective strategy in aligning P3HT NWs in the presence of PS and has a significant impact on the molecular order, morphology, and consequently charge transport. Shear-coated P3HT-NWs/PS nanocomposites consistently exhibited higher carrier mobilities compared to P3HT NWs or pristine P3HT/PS films by up to 10.2-fold. P3HT-NWs/PS nanocomposites containing only 3 wt % P3HT exhibit a mobility of similar to 0.053 cm(2) V-1 which-as comparable to that of the 30 wt % P3HT (0.064 cm(2) V-1 s(-1)) and even higher than that of 100 wt % P3HT (similar to 0.024 cm(2) V-1 s(-1))