Vanadium modified mesocellular silica foams (MCF) materials (V content ca. 3 and 5 wt%) prepared by the impregnation method show mainly isolated or low-polymeric VOx species, which was confirmed by means of Raman spectroscopy and DR UV-Vis. Textural measurements, and also XRD and TEM results indicate that the characteristic mesocellular structural features of MCFs are preserved after vanadium incorporation. The MCF-supported vanadia catalysts exhibit much higher propene conversion and propene oxide productivity when compared to vanadium modified mesoporous silicas of 2D structure, demonstrating that apart from the presence of highly dispersed isolated vanadium species, internal molecular transport within three-dimensional ultra large pores of MCF materials also plays an important role in gas-phase propene epoxidation. [GRAPHICS] .