A new electrochemical-chemical-electrochemical synthetic route to silver(I) chloride nanoparticle-polypyrrole composites is presented. The chemical precipitation of silver chloride particles inside a polymer matrix was studied at a selected oxidation level of the conducting polymer. Cyclic voltammetry and electrochemical impedance spectroscopy evidence chemical interaction between the two redox subsystems. The electrochemistry of the inorganic seeds of the composite was utilized to find out the best condition for the enhancement of the Raman signal of sodium benzoate in water. Scanning electron microscopy and atomic analysis of the organic-inorganic hybrid material deposited on platinum by electron diffraction spectroscopy were undertaken to follow the surface morphology and composition of the material. The sub-micrometer inorganic seeds of the composite deposited on a carbon fiber were shown by transmission electron microscopy to be composed of nanoparticles.