A blend of poly(3-hexylthiophene) (P3HT) and poly(n-hexyl isocyanate-block-2-vinylpyridine) (PHIC-b-P2VP) in a common solvent shows the formation of long-range (micrometer-scale) nanowires of P3HT through hydrophobic interactions between the hexyl arms of P3HT and PHIC in a parallel way, which increase the planarity that leads to the generation of vibration bands with a lower free exciton bandwidth (W = 67 meV) in the solution state, which is further decreased to 9 meV after 48 h annealing of the blend film. The resulting nanowires of the P3HT show a 100-fold increase in current in comparison to pristine P3HT.