A method to vary locally the physical properties of a porous material is presented. A wet gel is first prepared following conventional sol-gel techniques. The pore walls are derivatized by adding to the gelling solution a silane carrying a polymerizable moiety such as trimethoxysilylpropyl. The solvent of the wet gel monolith is then exchanged with a solution of a monomer such as styrene and a photoinitiator such as 2,2′-azobis-isobutyronitrile. Illumination with ultraviolet light initiates polymerization which in turn engages the moiety dangling from the pore surfaces. Supercritically dried monoliths were characterized with techniques such as field-emission scanning electron microscopy (SEM), methylmethacrylate atomic force microscopy (AFM), Fourier transform infrared (FT-IR) spectroscopy, and Brunauer-Emmett-Teller surface area measurements. These structural characterization techniques showed that the silica nanoparticles making up the backbone of the monoliths were cross-linked by a polymer conformal coating. Mechanical characterization was carried out with nanoindentation and the three-point flexural method and showed that the properties of uniformly photo-cross-linked monoliths could be varied by varying exposure time. So, for example, the monolith density could be varied between about 0.21 and 0.97 g • cm -3 , the porosity between 6 and 87%, and Young's modulus between 9 and about 1800 MPa. Overall, the characterization techniques show that photo-cross-linked monoliths have physical and mechanical properties comparable and often superior to those of monoliths obtained by thermally initiated cross-linking (see, for example,