Near-infrared Fourier transform Raman spectroscopy was used to study the surface-enhanced Raman spectroscopy (SERS) behavior of nicotinamide adenine dinucleotide (NAD) on a gold electrode. It was found that the quality of SERS can be largely improved by using a near-infrared laser as the exciting source. Many bands, which cannot be enhanced in conventional SERS excited by visible light, can be observed clearly in FT-SERS. The potential, pH, and concentration dependence of the SERS revealed that NAD adsorbed on a gold electrode can be opened to a certain extent. Either the adenine or the nicotinamide moiety may change their adsorption states during the potential scanning process. The FT-SERS of NAD exhibits quite different properties from conventional SERS in two aspects : (1) the spectrum is quite dependent on applied voltages not only in peak intensities, but also in band positions; in visible excited SERS, NAD and its analogues showed no potential dependence or only manifested changes in peak intensities; (2) a small peak coupled with the ring breathing vibration band of the nicotinamide moiety appeared and increased with a negative shift of the potential. In contrast, only a single peak for this mode appeared in visible excited SERS. In addition, a very interesting phenomenon was observed in that a group of new bands appeared in the positive potential region which are similar to those with NAD binding a dehydrogenase enzyme. These results imply strongly that a charged and roughened electrode may be useful as an artificial enzyme model.