In the present study, an experimental apparatus for laser spectroelectrochemical studies was developed. Laser-induced fluorescence spectroscopy and surface-enhanced resonance Raman spectroscopy were used in situ to study the electrochemical reduction process of alpha, beta, gamma, delta-tetra-(4-trimethyl ammonium phenyl) porphyrin. It was concluded that adsorbed porphyrins on the surface of an Ag electrode underwent partial incorporation of the porphyrin ring in the Ag. The electrochemical reaction of porphyrin on an Ag electrode was electroreduction, and the electroreduction of porphyrin occurred only in the porphyrin ring, and not on the substituents of the porphyrin.