Two new low-bandgap block copolymers derived from dithienylbenzothiadiazole (DTBT) and different electron-rich functional groups (dioctoxyl benzene and N-octyl-diphenylamine), poly(1,4-dioctoxyl-2,5-divinylbenzene-co-4,7-dithiophene-2'-yl-2,1,3-ben zothiadiazole) (PPV-DTBT), poly(3,8-divinyl-N-octyl-diphenylamine-co-4,7-dithiophene-2'-yl-2,1,3-be nzothiadiazole) (PDPAV-DTBT), were synthesized by Heck cross-coupling polymerization. PPV-DTBT and PDPAV-DTBT are easily soluble in common organic solvents such as o-dichlorobenzene and chloroform. DSC and TGA results indicate that these copolymers possess good thermal stabilities. PPV-DTBT and PDPAV-DTBT films exhibit broad absorption bands at 300-765 nm (with an optical bandgap of 1.62 eV) and 300-733 nm (with an optical bandgap of 1.69 eV), respectively. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of PPV-DTBT were estimated by cyclic voltammetry to be -5.43 and -3.74 eV, respectively, and the HOMO and LUMO of PDPAV-DTBT were -5.37 and -3.7 eV, respectively. Preliminary photovoltaic cells based on the composite structure of ITO/PEDOT: PSS/PPV-DTBT:PCBM (1: 2, w/w)/Al showed an open-circuit voltage of 0.75 V, a power conversion efficiency of 0.6%, and a short circuit current of 1.7 mA . cm(-2).