Charge transport properties of common donor copolymers in organic photovoltaics, poly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl}) (PTB7) and poly([2,6′-4,8-di(5-ethylhexylthienyl)benzo[1,2-b;3,3-b]dithiophene]{3-fluoro-2[(2-ethylhexyl) carbonyl]thieno[3,4-b]thiophenediyl}) (PTB7-Th), with molecular structures differing only in the pendant group, are studied. This is the first report of field-effect transistor mobility (µ FET ) of PTB7-Th (0.14 cm 2 V −1 s −1 ) and the highest µ FET for PTB7 (0.01 cm 2 V −1 s −1 ). µ FET of PTB7-Th is found to be almost one order of magnitude higher than PTB7. To understand the influence of molecular structure on charge transport, hole reorganization energy (λ h ) is calculated from first-principles. λ h of PTB7-Th (≈150 meV) is found to be lower than PTB7 (≈346 meV). Further, the ratio of hopping rate versus square of charge transfer integral calculated from Marcus theory using λ h for these systems is found to indicate a higher rate of hole transfer across dimers or homojunction interface for PTB7-Th. These results are supplemented by experimentally determined λ using bulk-heterojunction organic solar cells, where λ PTB7-Th ≈200 meV and λ PTB7 ≈310 meV follow a similar trend. The effective hole-mobility estimation from BHJ devices correlates well with these λ values. This study provides understanding of charge transport properties via reorganization energy, as a function of pendant group without altering the backbone of the chains. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim