A series of conjugated polymer bearing 4H-cyclopenta[def]phenanthrene (CPP) unit have been synthesized and was evaluated in bulk heterojunction solar cell. The alternating copolymers with CPP unit were incorporated with 4,7-dithienyl-2,1,3-benzothiadiazole (DTBT) unit by Suzuki conditions. The newly synthesized copolymers, poly(2,6-((4,4-bis(2-ethylhexyl)-4H-cyclopenta[def]phenanthrene))-alt-(4 ,7-((2-thienyl)-2,1,3-benzothiadiazole))) (PCPP-DTBT), and poly(2,6-(4,4-bis(4-((2-ethylhexyl)oxy)phenyl)-4H-cyclopenta[def]phenant hrene)-alt-(4,7-((2-thienyl)-2,1,3-benzothiadiazole))) (PBEHPCPP-DTBT), contain dialkyl and bis(alkoxyphenyl) groups in the CPP unit, respectively. The HOMO-LUMO energy bandgaps of these materials, estimated from UV-vis spectroscopy and cyclic voltammetry (CV), were 2.00 eV for PCPP-DTBT and 1.80 eV for PBEHPCPP-DTBT. Bulk heterojunction solar cells based on the blends of the polymers with [6,6]phenyl-C-71-butyric acid methyl ester (PC71BM) gave power conversion 2 efficiencies as 1.00% for PCPP-DTBT and 1.12% for PBEHPCPP-DTBT under AM 1.5, 100 mW/cm(2) (C) 2009 Elsevier Ltd. All rights reserved.