New donor-acceptor (D-A) conjugate polymers based on 3,6-bis(2-bromothieno-[3,2-b]thiophen-5-yl)-2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]-pyrrole-1,4-(2H,5H)-dione (Br-TTDPP) combined with three different electron-donating monomers bithiophene (BT), di(2-thienyl)ethene (TVT), and di(selenophene-2-yl)ethene (SVS) were synthesized. The optical band gap, electrochemical properties and organic field-effect transistor (OFET) device performance of the TTDPP-based polymers were systematically investigated. X-ray diffraction (XRD) was used to evaluate the molecular packing of the TTDPP-based polymers. Among three polymers, TTDPP-SVS showed the smallest d-spacing and the largest distance of 0.372 for π-π stacking. In particular, an OTFT having a TTDPP-SVS active layer showed the highest hole mobility of 0.196 cm2 V-1 s-1, the lowest threshold voltage down to -3.6 V, and the highest Ion/Ioff ratio of 6.5 × 104. This indicates that π-extended SVS significantly improves charge transport properties.