© 2016 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim A novel donor–acceptor type conjugated polymer based on a building block of 4,8-di(thien-2-yl)-6-octyl-2-octyl-5H-pyrrolo[3,4-f]benzotriazole-5,7(6H)-dione (TZBI) as the acceptor unit and 4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′]dithiophene as the donor unit, named as PTZBIBDT, is developed and used as an electron-donating material in bulk-heterojunction polymer solar cells. The resulting copolymer exhibits a wide bandgap of 1.81 eV along with relatively deep highest occupied molecular orbital energy level of −5.34 eV. Based on the optimized processing conditions, including thermal annealing, and the use of a water/alcohol cathode interlayer, the single-junction polymer solar cell based on PTZBIBDT:PC71BM ([6,6]-phenyl-C71-butyric acid methyl ester) blend film affords a power conversion efficiency of 8.63% with an open-circuit voltage of 0.87 V, a short circuit current of 13.50 mA cm−2, and a fill factor of 73.95%, which is among the highest values reported for wide-bandgap polymers-based single-junction organic solar cells. The morphology studies on the PTZBIBDT:PC71BM blend film indicate that a fibrillar network can be formed and the extent of phase separation can be manipulated by thermal annealing. These results indicate that the TZBI unit is a very promising building block for the synthesis of wide-bandgap polymers for high-performance single-junction and tandem (or multijunction) organic solar cells.