This unconventional dependence of thin film property on aggregate structure highlights the importance of investigating the precise structure of solution state, and the resulting assembly pathway of conjugated polymers. We believe that our findings have implications beyond charge transport, as the assembly pathways reported in this work can significantly impact other solidstate properties from charge generation, exciton, photon and spin transport, electromechanical response, to chemical-electrical signal transduction. Received: ((will be filled in by the editorial staff)) Revised: ((will be filled in by the editorial staff)) Published online: ((will be filled in by the editorial staff))