Highly conductive and transparent poly-(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) films, incorporating a fluorosurfactant as an additive, have been prepared for stretchable and transparent electrodes. The fluorosurfactant-treated PEDOT:PSS films show a 35% improvement in sheet resistance (R s ) compared to untreated films. In addition, the fluorosurfactant renders PEDOT:PSS solutions amenable for deposition on hydrophobic surfaces, including pre-deposited, annealed films of PEDOT:PSS (enabling the deposition of thick, highly conductive, multilayer films) and stretchable poly(dimethylsiloxane) (PDMS) substrates (enabling stretchable electronics). Four-layer PEDOT:PSS films have an R s of 46 Ω per square with 82% transmittance (at 550 nm). These films, deposited on a pre-strained PDMS substrate and buckled, are shown to be reversibly stretchable, with no change to R s , during the course of over 5000 cycles of 0 to 10% strain. Using the multilayer PEDOT:PSS films as anodes, indium tin oxide (ITO)-free organic photovoltaics are prepared and shown to have power conversion efficiencies comparable to that of devices with ITO as the anode. These results show that these highly conductive PEDOT:PSS films can not only be used as transparent electrodes in