In calcined and rehydrated VSiB zeolite prepared following a method described earlier, three kinds of tetrahedral VV species can be clearly identified by photoluminescence spectroscopy even at low V content, in contrast to V-51 NMR and diffuse reflectance UV-Visible spectroscopies which do not allow them to be distinguished. A comparative study by photoluminescence and V-51 NMR spectroscopies leads to the suggestion that there is a correlation between the vibrational energy of the V=O bond and the corresponding chemical shift of the V-51 NMR signal.