A fabrication of the surface-enhanced Raman scattering (SERS) active substrates has been developed by immersion
plating of the silver onto porous silicon (Ag-<i>por</i>-Si). Effects of the porous silicon morphology on the structure of the Ag
films have been analyzed by scanning electronic microscope. Activity of the Ag-coated por-Si toward SERS was
estimated using water-soluble porphyrins as analyte molecules. The Ag-<i>por</i>-Si samples were appeared to be sensitive
and stable SERS-active substrates. It has been found that the variation of SERS signal scanned over the sample surface is
less than 9%. Additionally, plates of Ag-<i>por</i>-Si displayed high sensitivity being stored within 1 month in the air. It was
shown that even several minutes incubation of Ag-<i>por</i>-Si in solution is enough to obtain well-defined SERS signal.
SERS spectra of the water-soluble cationic tetrakis(N-methylpyridyl)porphyrin (H<sub>2</sub>TMPyP4) and anionic
tetrakis(sulfonatophenyl)porphyrin (H<sub>2</sub>TPPS) were compared with their resonance Raman (RR) spectra. For the cationic
H<sub>2</sub>TMPyP4 the partial metallation has been detected during impregnation of the porphyrin molecules on the Ag-<i>por</i>-Si
surface. In case of the anionic H<sub>2</sub>TPPS there was no evidence of the silver complex formation.