We present detailed resonance Raman spectroscopic results excited at 220 and 287 nm for alumina-supported VOx catalysts. The anharmonic constant, harmonic wavenumber, anharmonic force constant, bond dissociation energy, and bond length chance in the excited state for double bonded V=O and single bonded V-O were obtained from fundamental and overtone frequencies. Totally symmetric and nontotally symmetric modes could be discerned and assigned on the basis of the overtone and combination progressions found in the resonance Raman spectra. Selective resonance enhancement of two different vibrational modes with two different excitation wavelengths was observed. This allowed us to establish a linear relationship between charge transfer energy and VO bond length and, consequently, to assign the higher-energy charge transfer band centered around 210-250 nm in the UV-vis spectra to the V=O transition.