In this publication, Wang et al. relate charge transport in Poly(3-Hexylthiophene) (P3HT) directly to its multiscale ordered structure. P3HT is one of the most prominent conjugated polymers, with applications from field-effect transistors to LEDs and solar cells. Charge carrier transport in P3HT is understood to relate to crystallinity, but typical thin films contain a mixture of phases. The authors use a preparation method that creates interconnected lamellae and removes all other phases of P3HT. Current mapping with PeakForce TUNA in conjunction with X-ray scattering and UV-VIS spectroscopy show that a contiguous network of edge-on, pi-stacked lamellae is key to long range charge transport. Formation of the optimized structure is related to processing conditions, indicating a potential path for improving performance of organic electronics devices.