Considering there is growing interest in the superior charge transport in the (E)-2-(2-(thiophen-2-yl)-vinyl)thiophene (TVT)-based polymer family, an essential step forward is to provide a deep and comprehensive understanding of the structure–property relationships with their polymer analogs. Herein, a carefully chosen set of DPP-TVT-n polymers are reported here, involving TVT and diketopyrrolopyrrole (DPP) units that are constructed in combination with varying thiophene content in the repeat units, where n is the number of thiophene spacer units. Their OFET characteristics demonstrate ambipolar behavior; in particular, with DPP-TVT-0 a nearly balanced hole and electron transport are observed. Interestingly, the majority of the charge-transport properties changed from ambipolar to p-type dominant, together with the enhanced hole mobilities, as the electron-donating thiophene spacers are introduced. Although both the lamellar d-spacings and π-stacking distances of DPP-TVT-n decreased with as the number of thiophene spacers increased, DPP-TVT-1 clearly shows the highest hole mobility (up to 2.96 cm2 V−1 s−1) owing to the unique structural conformations derived from its smaller paracrystalline distortion parameter and narrower plane distribution relative to the others. These in-depth studies should uncover the underlying structure–property relationships in a relevant class of TVT-like semiconductors, shedding light on the future design of top-performing semiconducting polymers.