Narrow band gap conjugated polymer zwitterions (CPZs) were synthesized by Suzuki polymerization and characterized to understand their electronic properties and utility as cathode modification layers in solar cells. The polymers were prepared from diketopyrrolopyrrole (DPP) and iso-indigo monomers containing sulfobetaine (SB) pendant groups, benefiting from an ion-rich aqueous phase in the polymerizations. UV-vis absorption spectroscopy revealed the optical energy gap value for the CPZs, ranging from 1.7 to 1.2 eV. Ultraviolet photoelectron spectroscopy of the CPZs as thin layers on Ag metal showed that the pendent zwitterions impart an interfacial dipole () to the metal and a work function reduction of approximate to 0.9 eV. OPVs fabricated using a conventional bulk heterojunction (BHJ) device architecture of ITO/PEDOT:PSS/(PTB7:PC71BM)/CPZ/Ag led to dramatic improvements in power conversion efficiency (PCE) values relative to devices having bare Ag cathodes (PCE<2% for bare Ag vs. 6.7-7.7% for CPZ/Ag). The benzothiadiazole (BT)/DPP polymer denoted as PT2BTDPPSB gave an optimal PCE of 7.7% in a conventional BHJ OPV device architecture fabricated on a Ag cathode. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 327-336