Recent advances in detector technology have enabled sensitivity limitations inherent in surface Raman scattering from thin organic films on metal surfaces to be overcome. The application of both surface enhanced Raman scattering and normal Raman scattering of organic monolayer films on metal surfaces in electrochemical and ambient environments is an area of active research in this laboratory. The use of surface selection rules for the development of detailed molecular pictures of these interfaces is discussed in this report. The application of these rules for determination of the orientation of self-assembled monolayers on Ag and Au surfaces in both electrochemical and ambient environments is used to demonstrate the approach. In addition, extension of surface Raman methods to the study of monolayer organic films on Pt surfaces is reported.