A water-soluble cationic polythiophene derivative, poly[3-(6-{4-tert-butylpyridiniumyl}-hexyl)thiophene-2,5-diyl] [P3(TBP)HT], is combined with anionic poly(3,4-ethylenedioxythiophene):poly(p-styrenesulfonate) (PEDOT:PSS) on indium tin oxide (ITO) substrates via electrostatic layer-by-layer (eLbL) assembly. By varying the number of eLbL layers, the electrode's work function is precisely controlled from 4.6 to 3.8 eV. These polymeric coatings are used as cathodic interfacial modifiers for inverted-mode organic photovoltaics that incorporate a photoactive layer composed of either poly[(3-hexylthiophene)-2,5-diyl] (P3HT) and the fullerene acceptor [6,6-phenyl-C61-butyric acid methyl ester (PC61BM) or the low bandgap polymer [poly({4,8-di(2-ethylhexyloxyl)benzo[1,2-b:4,5-b′]dithiophene}-2,6-diyl)-alt-({5-octylthieno[3,4-c]pyrrole-4,6-dione}-1,3-diyl) (PBDTTPD)] and the electron acceptor [6,6-phenyl-C71-butyric acid methyl ester (PC71BM)]. The power conversion efficiency (PCE) of the resulting photovoltaic device is dependent on the composition of the eLbL-assembled interface and permits the fabrication of devices with efficiencies of 3.8% and 5.6% for P3HT and PBDTTPD donor polymers, respectively. Notably, these devices demonstrate significant stability with a P3HT:PC61BM system maintaining 83% of its original PCE after 1 year of storage and a PBDTTPD:PC71BM system maintaining 97% of its original PCE after over 1000 h of storage in air, according to the ISOS-D-1 shelf protocol. ; peer reviewed: yes ; NRC Pub: yes