New random poly(benzo[1,2-b:4,5-b']dithiophene-thieno[3,4-c]pyrrole-4,6-dione-pyrrolo[3,4-c]pyrrole-1,4-dione} (PBDT-TPD-DPP) based on benzo[1,2-b:4,5-b]dithiophene (BDT) as donor and thieno[3,4-c] pyrrole-4,6-dione (TPD, 60-90%), pyrrolo[3,4-c]pyrrole-1,4-dione (DPP, 10-40%) as acceptors were synthesized through Stille coupling reaction. The photophysical, electrochemical and photovoltaic properties of random polymers were investigated. The random polymers with high molecular weight (M-n = 33.5-41.7 kDa) exhibited broad and strong absorption covering the spectra range from 350 nm up to 922 nm with absorption maxima at around 700 nm, the relatively deep highest occupied molecular orbital (HOMO) energy levels vary between -5.25 and -5.42 eV and suitable lowest unoccupied molecular orbital (LUMO) energy levels ranging from -3.85 to -3.91 eV. Polymer solar cells (PSC) based on these new random polymers were fabricated with device structures of ITO/PEDOT: PSS/random polymers: PC71BM (1:2, w/w)/Ca/Al. The photovoltaic properties of random polymers were evaluated under AM 1.5G illumination (100 mW/cm(2)). Devices based on the random polymers showed open circuit voltage (V-oc) of 0.71-0.83 V. and power conversion efficiency (PCE) of 0.82-1.80%. (C) 2012 Elsevier Ltd. All rights reserved.