Transition metal bis(acetylacetonate) complexes of Co(TI), Ni(II), Cu(II), and Zn(II) have been found to be active catalysts for the sol-gel process. The catalytic activity of these complexes decreases in going from Co(II) to Zn(II) and is highest for the acetylacetonate ligand system. Si-29 NMR studies show that the complexes act primarily as condensation catalysts and are, in that regard, similar to Bronsted bases such as hydroxide. Mechanistically, however, they appear to differ significantly from hydroxide in how they induce condensation. This is revealed in the catalyst concentration dependence, which is 1/2 order for the metal complexes and Ist order in hydroxide. Differences are also apparent in the thermochemical parameters that indicate that the metal complexes act to increase the entropy of the transition stale leading to condensation. The catalytic activity is proportional to the degree of ligand dissociation of the metal complex, and experiments suggest that the active catalytic species is specifically the first dissociation product, M-II(acac)(+).