© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Herein, this study investigates the impact of branching-point-extended alkyl chains on the charge transport properties of three ultrahigh n-type mobility conjugated polymers. Using grazing incidence wide-angle X-ray scattering, analysis of the crystallinity of the series shows that while π–π interactions are increased for all three polymers as expected, the impact of the side-chain engineering on polymer backbone crystallinity is unique to each polymer and correlates to the observed changes in charge transport. With the three polymers exhibiting n-type mobilities between 0.63 and 1.04 cm2 V−1 s−1, these results ratify that the indolonaphthyridine building block has an unprecedented intrinsic ability to furnish high-performance n-type organic semiconductors.