A series of novel thiophene- and selenophene-based low-bandgap polymers were synthesized using a Stille cross-coupling reaction; these polymers contained quinoxaline and diketopyrrolopyrrole as acceptors. Various acceptors were introduced into the selenophene backbones, and the solubility, absorption spectra, energy levels, charge transport, blend film morphology, and photovoltaic properties of the resulting polymers were investigated. The weight-averaged molecular weights (Mw) of P3TDTQ, P3SDTQ, P3TDTDPP, and P3SDTDPP were found to be 12 300, 15 500, 13 300, and 17 200, with polydispersity indices of 1.46, 1.85, 1.58, and 1.63, respectively. Photophysical studies revealed low bandgaps of 1.70 eV for P3TDTQ, 1.63 eV for P3SDTQ, 1.27 eV for P3TDTDPP, and 1.25 eV for P3SDTDPP; the films could harvest a broad solar spectrum, covering the range from 300 to 800 nm (P3TDTQ and P3SDTQ) and from 350 to 950 nm (P3TDTDPP and P3SDTDPP). Solution-processed field-effect transistors fabricated from these polymers had p...