Materials derived by precipitation or polymerization chemistry (e.g., “sol-gel” methods) are usually obtained in noncrystalline or otherwise metastable phases, and transformation to more thermodynamically stable phases generally occurs by a nucleation and growth process. In a fully reconstructive transformation, such as occurs in the alumina system, the activation energy for nucleation may be higher than that for simple short-range diffusion. Hence nucleation frequency can be a controlling factor in the development of microstructurc. The efficacy of seeding as a method of microstructural and phase control in solution-derived or so-called sol-gel materials has been clearly demonstrated for the alumina system. The epitaxial nature of this phenomenon is explored, using the polarizing microscope to follow the crystallographic orientation of the transformed material as the transformation proceeds, showing that this is epitaxial in nature, and that the nucleation frequency in unseeded material is relatively low (∼ 1010 cm−3). The microscope was then used to demonstrate the effect on nucleation frequency of seeding with materials selected to be isostructural, isotypic, and having little or no similarity to the corundum structure. Using these and other methods, the seeding phenomenon in alumina gels is shown to result from epitaxial growth of the stable corundum phase on isostructural or isotypic nuclei in the solid state. This approach is applied to formulate hypotheses for the mechanisms by which some of the previously reported effects of seeding, e.g., enhanced densification and microstructural refinement, can be understood and to formulate a set of generalizations for its potential application to other systems.