Surface-enhanced Raman spectra (SERS) are reported for nicotinamide adenine dinucleotide (NAD+, oxidised form) adsorbed on colloidal silver at concentrations between 10–3 and 10–5 mol dm–3, and using various excitation wavelengths. Adenosine diphosphate (ADP) gave an SER spectrum similar to that of NAD+, except for the absence of the nicotinamide SER band observed for NAD+ at 1030 cm–1. NADH (reduced form of NAD+) did not give an SER spectrum at the alkaline pHs necessary to prevent decomposition. No SER spectrum was obtained for NAD+ when bound to the enzyme GAPDH; the NAD+ is too deeply buried in the protein for effective surface enhancement. The applicability of the surface selection rules arising from the electromagnetic enhancement mechanism to determine NAD+ orientation at the silver surface is discussed in the light of the probable contribution to SERS intensity from a charge-transfer mechanism. While the selection rules do not, in this case, appear useful for determining NAD+ orientation at silver, wavenumber shifts do indicate surface interaction with N1 of adenine. The general surface geometry of NAD+ adsorbed on silver at low ( < 10–4 mol dm–3) concentrations is deduced as being extended, with phosphate groups binding directly to silver, and ribose, nicotinamide and adenine moieties all in close proximity to the surface.