We describe the electrochemical synthesis of silver oxide nanowires and nanowire bundles, filled platelets and hollow microplatelets in either basic or acidic N,N-dimethylformamide solution. We propose that these nanostructures are formed at the electrode surface via two competing reactions namely, silver dissolution off the electrode in the presence of NH3 or HF during the anodization of silver, and silver oxide precipitation. Results show that the precipitated silver oxide nanoparticles aggregate into nanowires as well as into filled and hollow microscale platelets, depending upon the nuclei concentration and the anodization current density. X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDX) and Raman scattering spectroscopy show that the nanowires and microplatelets are mainly composed of Ag2O. Nanowire bundles are used as substrates for surface-enhanced Raman scattering (SERS) where single molecule detection is achieved and evidenced using a bianalyte Raman technique.