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We report a facile approach that could provide a significant enhancement in charge transport of the conjugated polymer/reduced graphene oxide (rGO) composite films using a non-solvent vapor treatment. As the methanol vapors were exposed to the poly(3-hexylthiophene) (P3HT)/rGO composite solution, P3HT chains self-assembled to create nanofibrillar structures via favorable π-π interactions. The π-π staking in P3HT was occurred by the non-solvent vapor exposure to minimize unfavourable interactions of P3HT chains to the non-solvent vapor molecules. The self-assembly of P3HT chains was more facilitated by the presence of rGO, because the surface of rGO can serve as nucleation sites for the growth of P3HT nanowires. Consequently, P3HT/rGO composite films obtained from the methanol vapor treated corresponding solutions exhibited a high charge carrier mobility (1.3 x 10-1 cm2 V-1 s-1), which is approximately 11-fold and 6.5-fold higher than those of pristine P3HT and P3HT/rGO composite films (1.2 x 10-2 cm2 V-1 s-1 and 2.0 x 10-2 cm2 V-1 s-1, respectively).