This paper presents a study of surface enhanced Eaman scattering (SEES) spectra of piperidine adsorbed on a silver electrode surface in the methanol solution. The potential dependence of the SEES spectra and SEES spectra of piperidine during two kinds of the Oxidation-reduction cyclic pretreatment of the silver electrode are measured. We have studied the relationship of SEES of piperidine in the methanol and aqueous system. The experiments show that the enhancement factor of SEES of piperidine in methanol system is smaller than that in the aqueous system and their potential dependence is different.