New methods were developed to prepare silver-doped sol-gel films for surface-enhanced Raman spectroscopy (SERS) applications. First, silver ions were doped into a sol-gel matrix. The doped silver ions were reduced into corresponding silver metal particles by two reductive procedures; chemical reduction and thermal reduction. The SERS spectra of benzoic acid were used to demonstrate the SERS effect of the new substrates. The adsorption strength of benzoic acid adsorbed on differently reduced substrates was discussed. The possible adsorption form and the orientation of adsorbate were also discussed.