With the growing interest in the superior charge transport in the (E)-2-(2-(thiophen-2-yl)-vinyl)thiophene (TVT)-based polymer, an forward step is to provide a comprehensive understanding of the structure-property relationships of their polymer analogs. Here, a set of DPP-TVT-n polymers are reported, involving different thiophene content in the diketopyrrolopyrrole(DPP)-TVT repeating units, where n is the number of thiophene spacer units. Their OFET characteristics demonstrate ambipolar behavior; with no spacer, the charge transports are observed nearly balanced, but with the electron-donating spacer, the majority of the properties changed from ambipolar to p-type dominant with enhanced hole mobility. Although both the lamellar d-spacings and π-stacking distances decreased with the number of spacers, DPP-TVT-1 shows the highest hole mobility due to the unique structural conformations derived from its smaller paracrystalline distortion parameter and narrower plane distribution.