High-quality Fourier transform surface-enhanced Raman scattering (FT-SERS) of a dilute solution of nicotinamide adenine dinucleotide (NAD) was recorded on a roughened Au electrode. It was found that the detection limit-could be lower as much as 3 orders of magnitude by using a near-infrared laser as the exciting source and an in-situ roughening technique. The SERS of NAD shows a strong potential dependence in the non-Faradaic regions. In regions of positive electrode potential, only the bands responsible for the adenine and nicotinamide moieties can be observed. In contrast, with a negative shift of the potential, several additional strong bands representing the ribose and phosphate moieties are also evident. Based upon the SERS behaviors of NAD in the regions of different potential, an adsorption mechanism for dilute NAD on the gold electrode was proposed. With this mechanism, the stacked NAD molecule is considered to be opened to some extent on an electric charged electrode. Specifically, under sufficiently negative potential, the NAD molecule appears to exist in a well-extended state on the gold electrode, leading to the tight adsorption of the entire NAD molecule on the electrode.