We demonstrate the use of poly(sulfobetaine methacrylate) (PSBMA), and its pyrene-containing copolymer, as solution-processable work function reducers for inverted organic electronic devices. A notable feature of PSBMA is its orthogonal solubility relative to solvents typically employed in the processing of organic semiconductors. A strong permanent dipole moment on the sulfobetaine moiety was calculated by density functional theory. PSBMA interlayers reduced the work function of metals, graphene, and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) by over 1 eV, and an ultrathin interlayer of PSBMA reduced the electron injection barrier between indium tin oxide (ITO) and C-70 by 0.67 eV. As a result, the performance of organic photovoltaic devices with PSBMA interlayers is significantly improved, and enhanced electron injection is demonstrated in electron-only devices with ITO, PEDOT:PSS, and graphene electrodes. This work makes available a new class of dipole-rich, counterion-free, pH insensitive polymer interlayers with demonstrated effectiveness in inverted devices.