The use of surface‐enhanced Raman scattering as a tool for the elucidation of reaction mechanisms in heterogeneous catalysis is investigated. Following a short survey of surface analytical techniques, the advantages of surface Raman spectroscopy are discussed. Submonolayer sensitivity is achieved by making use of the surface enhancement effect. Adsorption and desorption phenomena of amines, which are of importance for catalytic dehydroamination reactions on copper surfaces, are studied using enhanced Raman scattering. Two models for the bonding of the amine to the surface are tested, by comparing the surface spectra with those of model compounds. Experiments are carried out on copper foils roughened by chemical etching, which exhibit strong surface enhancement. The design of the substrates is guided by advances in modeling the electromagnetic enhancement contribution. In particular the influences of particle size and of dipolar interactions between the particles on a surface must be taken into account.