Alternating donor-acceptor type copolymers, poly[{5,11-di(9'-heptadecanyl)indolo[3,2-b]carbazole}-alt-{2,5-di(thiophen-2-yl)thiazolo[5,4-d]thiazole-5,5'-diyl}] (PIC-TZ) and poly[{6,6',12,12'-tetraoctylindeno [1,2-b] fluorene}-alt-{2,5-di(thiophen-2-yl)thiazolo[5,4-d]thiazole-5,5'-diyl}] (PIF-TZ), were synthesized and examined for applications in polymeric photovoltaic cells. The polymers have a fused coplanar main backbone with good planarity for intermolecular packing and high charge mobility. The indolocarbazole and indenofluorene units contain two or four binding sites for alkyl substituents that have pronounced solution processiblity compared to the carbazole and fluorene moieties. The number-average molecular weights (M(n)) of the synthesized polymers were determined to be 11,000 g/mol (PDI = 2.27) for PIC-TZ, and 17,000 g/mol (PDI = 1.77) for PIF-TZ. The optical band gap of PIC-TZ and PIF-TZ in film was determined to be 2.14 eV and 2.21 eV, respectively, and an electrochemical study confirmed the desirable HOMO/LUMO levels of the copolymers, which enabled efficient electron transfer and a high open circuit voltage (V(OC)) when blending them with fullerene derivatives. The space charge limited current mobility measurements showed a hole mobility of 10(-3) cm(2) V(-1) s(-1) for the copolymers. When the polymers were blended with [6,6] phenyl-C(61)-butyric acid methyl ester (PCBM), PIC-TZ showed the best performance with V(OC), short-circuit current and power conversion efficiency of 0.86 V, 4.16 mA/cm(2) and 1.64%, respectively, under AM 1.5G illumination conditions (100 mW cm(-2)). (C) 2011 Elsevier B. V. All rights reserved.