We have used Stille coupling polymerization to synthesize new crystalline deep HOMO level polymers, PhBDT-BT and PhBDT-DTBT, which consist of 4,8-bis(2-octyldodecyloxyphenyl)-benzo-[1,2-b:4,5-b'] dithiophene (PhBDT) as an effective electron donor unit and 4,7-dibromobenzo [c] 11,2,51 thiadiazole (BT), or 4,7-bis(5-bromothiophen-2-yl)benzo[c] [1,2,5] thiadiazole (DTBT) units as electron acceptor units. Both polymers exhibited a low-lying highest occupied molecular orbital (HOMO, -5.43 for PhBDT-BT, -5.66 eV for PhBDT-DTBT) to obtain a high open circuit voltage (V-oc). The band gaps of PhBDT-BT and PhBDT-DTBT were tuned to 1.72 and 1.69 eV, respectively. As a result, bulk heterojunction photovoltaic devices derived from these polymers and fullerenes provided open-circuit voltages (V-oc) as high as 0.73 for PhBDT-BT/PC70BM (1:2) and 0.86 V for PhBDT-DTBT/PC70BM (1:2). In particular, photovoltaic devices fabricated from the PhBDT-DTBT/PC70BM (1:2) blend system exhibited an excellent photovoltaic (PV) performance with a 170 c value of 0.73 V, a short-circuit current density (J(sc)) value of 7.06 mA/cm(2), a fill factor (FF) value of 0.67, and a promising power conversion efficiency (PCE) of 3.5%. In addition, organic thin film transistor (OTFT) devices using PhBDT-DTBT as the semiconductor also showed excellent performance with a value of hole mobility of 4.7 x 10(-2) cm(2) V(-1)s(-1). In the PhBDT-DTBT, the thiophene bridge between the PhBDT and benzthiadiazole provides enough space for the intedigitaion of the bulky alkoxyphenyl side chains, increasing the planarity with enhanced pi-pi stacking. (C) 2014 Elsevier B.V. All rights reserved.