Herein, silver nanowires with high surface roughness are prepared via vacuum thermal evaporation and a solid-state ionics method. The nanowires are assembled into silver conductor RbAg4I5 films under the imposed current intensity, obtaining surface-enhanced Raman scattering (SERS) substrates with highly uniform, well ordered, and high-repeatability. The surface enhanced Raman characteristics of the silver-nanowire substrates with high surface roughness are detected using Rhodamine 6G (R6G) probe molecules in aqueous solution. The experimental results show that the prepared silver nanowires are branch-shaped and orderly arranged in the macro and micro structures, respectively; the fractal dimension of the silver nanostructure is 1.59. The method detects molar R6G concentration as low as 10 -17 mol/L when the silver nanowires are used as SERS substrates. The prepared silver nanowires with orderly dense arrangement and high surface roughness confirm its potential applicability in environmental sciences and other fields.