This study provides insights into the complex interplay between the microstructure and electrical properties of conjugated polymers, which serve as the cathode material for lithium-sulfur batteries. Specifically, the effects of polymer chain regioregularity on the morphology and the polymer's electronic structure and charge transfer properties are demonstrated. Our work thus highlights the importance of polymer regularity and morphology modifications to design high-mobility crystalline phases, which would optimize the electrochemical performance of the cathode material.