We have discovered and developed a process where positive relief structures in silica sol-gel films can be made using electron beam writing methods. Electron beam cured sol-gel structures have been made that have lateral and vertical dimensions both on the micron and nanometer scales. The sol-gel structures can be used as etch masks or deposition masks on substrates or can be used directly as positive relief molds for embossing the micro- or nanoscale features into other materials.