A novel electron-deficient building unit, dithienylthienothiophenebisimide, and its polymers (PTBIs) are reported. Organic photovoltaic (OPV) cells based on PTBIs as p-type material exhibit 8.0% efficiencies with open-circuit voltages higher than 1 V. Interestingly, PTBIs also function as n-type material in OPVs depending on the molecular structure. These polymers also exhibit p-channel, n-channel, and ambipolar behaviors in field-effect transistors.