Silver(I) halide particles embodied in polypyrrole matrices are synthesized and further processed electrochemically to get nanoparticles of silver with significant activity in the surface-enhanced Raman spectroscopy (SERS) of the rhodamine 6G test solute, which is considered as a clear evidence of Ag nanocrystallization. The electrocrystallization of Ag nanoparticles is analyzed using redox charges of composites determined from cyclic voltammograms recorded at various time scales and/or cycle numbers. Pristine PPy/AgX and modified PPy/AgX/AgNP composites are characterized using electrochemical impedance spectroscopy, scanning electron microscopy, and X-ray electron dispersive spectroscopy. The thermodynamic and kinetic conditions of the electrochemical modification of pristine polypyrrole–AgX composites leading to the electrocrystallization of Ag nanoparticles are discussed.