Processing-microstructure relationships in a silica gel system, based on mixtures of colloidal sol and soluble potassium silicate, have been studied. Quantitative microstructural information regarding colloidal cluster sizes, size distributions, surface areas, and pore-size distribution from the nanopore range to the macropore range was determined via small-angle scattering and transmission electron microscopy. The colloid cluster size distribution varies systematically, with gels fabricated with the least colloidal fraction possessing the most polydisperse microstructure. It is shown that the porosity over the entire range can be tailored by selecting the appropriate starting chemistry; under the same pH conditions, the ratio of the two silicate ingredients controls the average size, the polydispersity of sizes, and the connectivity of the pores. A population of fine (2 nm) uniformly dispersed nanopores, which result from leaching, is responsible for large increases in surface area. The leaching process can be controlled by the surrounding macropore void size, which determines alkali transport. The product material consists of 85% large, open pores, with fine pores within the gel skeleton, making this gel an ideal candidate for controlled-porosity applications such as catalyst supports and magnetic composites.