An ambient pressure method for drying sol-gel materials has been used to synthesize highly porous vanadium oxide and molybdenum oxide materials with aerogel-like properties. The resulting solids exhibit 80-90% porosity and high surface area (150-280 m(2)/g). The synthesis approach uses liquid exchange to replace the pore fluid with a low surface tension, nonpolar solvent that reduces the capillary pressures developed during drying. The technique is adaptable to the preparation of porous thin films.