Simultaneous LSPR and electronic sensing of potential induced ion adsorption onto gold nanowire arrays is presented. The formation of a Stern layer upon applying an electrochemical potential generated a complex optical response. Simulation of a lossy atomic layer on the nanowire array using the Multiple Multipole Program (MMP) corresponded very well to the experimentally observed peak position, intensity, and radius of curvature changes. Additionally, a significant voltage-dependent change in the resistance of the gold nanowire array was observed during the controlled formation of the electrical double layer. The results demonstrated that an applied electrochemical potential induces measurable changes in the optical and electrical properties of the gold nanowire surface. This is the first demonstration of combined plasmonic and nanowire resistance-based sensing of a surface process in the literature.