The adsorption of pyridine onto silver colloids has been investigated by Raman spectroscopy experiments and by ab initio DFT and MP2 calculations. The solvation dynamics of the pyridine in water has been studied by a molecular dynamics simulation. The results are compared with the latest available experimental and theoretical data. It is found that the pyridine is essentially hydrogen bonded to one solvent molecule. Calculations based on pyridine-water and pyridine-Ag(+) complexes allow the reproduction of the experimentally observed Raman features and explain the adsorption process of the ligand in silver hydrosols.