The synthesis of a novel fused hexacyclic electron rich monomer incorporating thieno[3,2-b]thiophene is reported and characterized by single crystal X-ray diffraction. Suzuki co-polymerization with benzothiadiazole (BT) afforded a novel low band-gap polymer P4TBT with high molecular weights and good solution processability. Bulk heterojunction solar cell devices using the P4TBT and [70]PCBM gave power conversion efficiencies of 2.5%. Top-gate, bottom-contact field effect transistors (FETs) using P4TBT displayed high hole mobilities of 0.07 cm(2).Vs(-1) demonstrating the suitability of the novel monomer and polymer for use in high performing organic electronic devices.