In this study, a method for the formation of type II trans-crystals of highly conjugated regioregular poly(3-butylthiophene-2,5-diyl) (P3BT) and poly(3-hexylthiophene-2,5-diyl) (P3HT) through a solution crystallization process on a carbon nanotube fiber reinforcing agent has been developed. Factors such as solvent selection, polymer concentration, and vapor pressure conditions were varied to investigate mechanisms behind the assembly process for both polymer transcrystals. Macrostructures were observed to be successfully assembled under high vapor pressure conditions through characterization with optical and atomic force microscopy. Negative birefringence was observed through polarized optical microscopy as a result of lamellar alignment perpendicular to the fiber nucleating agent. Charge carrier mobility within the polymer structure is characterized by conductive atomic force microscopy and is believed to be directionally dependent based on the orientation of lamellar alignment. The facile fabrication and enhanced electrical properties of these highly ordered transcrystal structures lead to promising opportunities for their future use in flexible electronic devices.