A highly efficient and eco-friendly protocol for the synthesis of an altating copolymer poly(7,7′-diazaisoindigo-alt-(E)-1,2-bis(3,4-difluorothien-2-yl)ethene) (PAIID-4FTVT) via direct arylation polycondensation (DArP) is presented. Through detailed study, we found that the inhibitory effect of 7,7′-diazaisoindigo on DArP stemmed from the coordination of N atom with catalyst can be overcome by using dimethylacetamide (DMAc) as the co-solvent. Thus, PAIID-4FTVT with number-average molecular weight (Mn) ＞ 100 kDa was synthesized via DArP by optimizing the content of DMAc. Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectroscopy revealed that PAIID-4FTVT was defect-free. Top gate and bottom contact (TG/BC) organic thin-film transistors (OTFTs) were fabricated to characterize the semiconducting properties of the polymers. PAIID-4FTVT displayed unipolar n-type characteristics with the electron mobility (μe) strongly dependent on Mn. The highest μe up to 0.25 cm2·V-1·s-1 was achieved with the high molecular weight sample.