Vanadium oxide supported on porous clay heterostructures (PCH) catalysts have been synthesized, characterized and evaluated in the selective oxidation of H2S to elemental sulfur. The catalysts were characterized by XRD, adsorption-desorption of N2 at -196 ºC, diffuse reflectance UV-Vis, H2-TPR, Raman spectroscopy and XPS. The catalysts with higher vanadium content are more active and selective, exhibiting a H2S conversion close to 70% after 360 hours on stream with a high selectivity towards elemental sulphur and a low formation of undesired SO2. The catalysts with V2O5 crystallites have shown a higher activity and resistance to the deactivation. The analysis of the spent catalyst has revealed the formation of V4O9 crystals during the catalytic test, which has been reported as the active phase in the selective oxidation of the H2S.