Framework-incorporated vanadium mesoporous silica materials with different contents in vanadium were obtained by a facile, direct synthesis at room temperature, using VOSO4 x 5H2O as the vanadium precursor. The porous characteristics of the samples and the coordination environment of the vanadia in the structure were studied by a combination of techniques: X-ray diffraction, N2-adsorption/desorption, FT-Raman, FTIR-PAS and UV-Vis-DR, electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) spectroscopy. A structural comparison is made using pulsed EPR and ENDOR spectroscopic techniques between vanadia deposited on the surface of MCM-41 by the Molecular Designed Dispersion method and as-synthesised samples of vanadia incorporated in the mesoporous silica framework using the above-mentioned synthesis method. The EPR study on the non-calcined samples proves the incorporation of a high amount of vanadium in the silica framework by the observation of a strong hyperfine coupling of the unpaired electron with 29Si. It demonstrates the feasibility for EPR to reveal structural information on true incorporation of metal ions in framework positions leading to metal oxides.