The surface chemistry of adsorbed isopropoxy groups on supported vanadia–alumina and vanadia–silica catalysts was investigated with multiple in situ spectroscopic techniques. The in situ FT-IR, Raman and UV–vis spectroscopic measurements provided molecular level information about the surface intermediates and the surface vanadium oxide species as a function of different conditions. The spectroscopic insights were compared to the steady state fixed bed catalytic reaction studies of isopropanol oxidation and propane oxidative dehydrogenation in order to better understand the molecular structure–reactivity/selectivity relationships.