The solid-state reaction of the ZSM-5 zeolite with V2O5 has been investigated by means of photoluminescence spectroscopy in combination with other spectroscopic techniques such as XAFS (XANES and FT-EXAFS), UV-vis, ESR, and FT-IR. It has been found that this reaction leads to the formation of the VO2+ species as well as the vanadium oxide species, (Si-O)(3)V=O, which has a C-3v symmetrical geometry and is located at two different sites, i.e., at positions accessible to small molecules as well as at inaccessible positions. These vanadium oxide species formed in the zeolite exhibits unique and specific photocatalytic reactivity toward the isomerization of cis-2-butene at 273 K.