This article describes the analytical methods for analyzing surfaces for corrosion and corrosion inhibition processes as well as failure analysis based on surface structure and chemical identity and composition. The principles and applications of the surface-structure analysis techniques, namely, optical microscopy, scanning electron microscopy, scanning tunneling microscopy, and atomic force microscopy, are reviewed. The article discusses the principles and applications of chemical identity and composition analysis techniques. These techniques include the energy dispersive X-ray spectroscopy, Auger electron spectroscopy, X-ray photoelectron spectroscopy, ion scattering spectroscopy, reflectance Fourier transform infrared absorption spectroscopy, Raman and surface enhanced Raman spectroscopy, and extended X-ray absorption fine structure analysis.