Gelation times of tetraethyl orthosilicate-derived sols containing selected di-to tetravalent cations as dopants were noted at different temperatures (15"-50"C). An analysis of these data, in conjunction with relevant published information, led to the tentative conclusions that (i) unhydrolyzed cations in bare form linked negatively charged silicate polymers in sols, thereby accelerating galation and (ii) hydrolyzed cations retarded the process by offering molecular size-related hindrance and competition for the available water for hydrolysis.