The Ag – pyridine system has been investigated by Surface Enhanced Raman spectroscopy (SERS), Raman and Nuclear Magnetic Resonance (NMR) spectroscopy. Raman and NMR spectroscopy data concerning the formation of a pyridine complex with silver cations in the solution bulk have been used to explain the nature of a band at 1025 cm-1 appearing in the SERS spectrum at the anode etching of a silver electrode. The existence of two complexes of different stoichiometric composition Ag(py)+ and Ag(py)2+, has been confirmed. The distribution of pyridine forms at Ag:py mole ratios from 0 to 6 has been obtained from the analysis of the intensities of individual components of the Raman spectrum. Both types of complexes have been shown to exist in solution at equimolar 1:1 ratio. It has been assumed that a complex of 1:1 composition will be adsorbed at the excess of Ag+ ions near the surface.