Thiophene small novel branched structures have been proposed as candidates for dopant agents transporting holes-electron in organic solar cell (OSC). Low-band gap of these branched oligotiophene have been obtained to be used in organic solar cells. Two branched thiophene oligomers, a sexithienylene vinylene (E)-Bis-1,2-(5,5´´-Dimethyl-(2,2´:3´,2´´-terthiophene) vinylene, (BSTV) and octathienylene vinylene (BOTV) (E)-Bis-1,2-(5,5´´´-Dimethyl-(2,2´:5´,2´´:3´,2´´´-tetrathiophene) vinylene oligomers, have been synthesized and used as electron donor or dopant in a bulk heterojunction poly(3-hexylthiophene) (P3HT), /[6,6]-phenyl C61-butyric acid methylester (PCBM), Organic Photovoltaic cell.