Nanotopography is known to affect cell response, but the mechanisms are unknown. It is therefore important to be able to produce biomaterial surfaces with controllable nanopore sizes and morphologies from materials that can be used to make templates (scaffolds) for tissue regeneration. A rapid method of fabrication of sol-gel monoliths with controlled nanopore size is described in this paper. Pores of 2 nm in diameter were achieved, termed micropores by IUPAC convention. Conventional sol-gel processing yields pores an order of magnitude larger. Gelling time was also reduced from many hours to a few minutes, without using a gelling agent, and large crack-free monoliths were synthesized within 1 week.