The surface specificity of vibrational sum frequency generation (VSFG) spectroscopy allows one to characterize adsorbed and reacting molecules on catalyst surfaces while the catalyst functions at high pressure and high temperature. VSFG spectroscopy can be carried out in different modes, including scanning, broadband, time-resolved, and polarization-dependent, and has been applied to various active surfaces. Single-crystal and nanoparticle model catalysts have mostly been used, which are typically prepared under ultrahigh vacuum, but applications to powder materials have been reported recently. In this article, the fundamentals and technical aspects of VSFG are summarized, and its benefits are illustrated by case studies of elementary processes of heterogeneous catalysis.