The combined use of DR-UV-vis and Raman spectroscopies allows one to evidence three kinds of tetrahedral V-V with different structure in V(x)SiBEA zeolite. In all cases, vanadium species possess distorted tetrahedral configuration. At very low vanadium content (0.05 wt %), the majority of tetrahedral V(V) species are strongly distorted and have a nonhydroxylated pyramidal structure (SiO)(3)V=O with V=O stretching at 1054 cm(-1) whereas the remaining tetrahedral V(V) species are less distorted with a hydroxylated pyramidal structure (SiO)(2)(HO)V=O with V=O stretching at 1018 cm(-1). In contrast, at higher vanadium contents (0.2-2 wt %), the main distorted V(V) species possess a nonhydroxylated pyramidal structure (SiO)(3)V=O with V=O stretching at 1033-1036 cm(-1). Periodic density functional theory (DFT) calculations confirm the presence of at least two different types of V site in V-containing zeolites. The experimental Raman bands recorded for V(x)SiBEA with low and high V content were confirmed on the basis of DFT calculations related to seven vanadium model sites. The difficulty to assign the vibrations in V-containing silica materials is due to the overlap of the different critical vibrational fingerprints (V=O, and Si-U-V vibration modes). Moreover, it was found that H-bond formation with a V=O group is not energetically favorable.