Two new donor-acceptor conjugated polymers, i.e. PB(C12DTP)V-DTDPP-C12 and PB(C12DTP)V-DTDPP-C12C8, were prepared by the Stille coupling of (E)-1,2-bis(4-dodecyl-6-(trimethylstannyl)-4H-dithieno[3,2-b:2′,3′-d]pyrrol-2-yl)ethene (Sn-B(C12DTP)V) with 3,6-bis(5-bromothiophen-2-yl)-2,5-didodecylpyrrolo[3,4-c]pyrrole-1,4-dione (Br-DTDPP-C12) and 3,6-bis(5-bromo-thiophen-2-yl)-2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4-dione (Br-DTDPP-C8C12), respectively. The molecular weight and thermal properties of the obtained polymers were characterized by gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermogravimetry (TG). Their optical and electrochemical properties were analyzed by UV-vis-NIR spectroscopy and cyclic voltammetry (CV). The morphological and molecular-packing features of the polymers were characterized by optical microscopy and atomic force microscopy (AFM), UV polarization spectroscopy and grazing incidence X-ray diffraction (GIXD) to determine the relationship between the structural morphology and the performance. PB(C12DTP)V-DTDPP-C12C8 with branched C12C8 side chains on DPP units shows much higher hole mobility (1.2 cm2 V-1 s-1) than 0.69 cm2 V-1 s-1 of PB(C12DTP)V-DTDPP-C12.