A series of chromium-containing mesocellular silica foam (MCF) catalysts have been prepared and characterized in the oxidative dehydrogenation (ODH) of propane between 350 and 600 degrees C. It is demonstrated that the chromium catalysts supported on MCF exhibit much higher catalytic activity in terms of propane conversion and propylene yield than literature results obtained over chromium-supported mesoporous SBA-15 or MCM-41 catalysts during the ODH of propane. Enhanced catalytic performance of the chromium-containing mesoporous MCF catalysts has been attributed to the unique three-dimensional (3D), continuous, ultralarge mesopore structure of the MCF materials, which allow a much faster internal molecular transport during the ODH of propane.