Silver nanowires are attractive components for a number of materials and applications, including silver nanowire (AgNW)-polymer composites, electrically conductive coatings, and transparent electrodes. In this manuscript, the ability of thiols with hydrophobic to ionic end groups to bind to AgNW surfaces is investigated, followed by how the polarity of the surface modifying thiol influences the morphological and electrical properties of both AgNW/PEDOT:PSS blend films and pure AgNW networks. Utilizing surface modification of AgNWs with sodium 3-mercapto-1-propanesulfonate (MPS), morphologically homogeneous AgNW/PEDOT:PSS thin films with an order of magnitude lower sheet resistance at similar transmittance values than unmodified AgNWs are obtained with a one-step processing method. Brief optimization of MPS-AgNW/PEDOT:PSS blends yields a sheet resistance of 22.6 Ω/□ at 81.4% transmittance.