The light beating technique (intensity correlation algorithm) was employed to analyze the Rayleigh scattering from the roughened Ag electrode in very dilute (10−4 M) pyrazine, pyridine and piperidine aqueous solutions containing KC1 (0.1 M). The relaxation time is longer when the applied voltages are between −0.4 V and −0.8 V (vs. SCE) where the Raman effect also shows greater surface enhancement. Also observed was that for the piperidine case the relaxation time reaches its maximum at the more negative applied voltage. The origin of the relaxation is attributed mainly to the desorption process of the pyrazine, pyridine and piperidine molecules off the roughened Ag electrode. An electrostatic model was also proposed for the interpretation of these experimental observations.