Insight into the factors that control the formation and size of heavy metal phosphate nanophases in vitreous silica has been gained by combining conventional and anomalous small angle x-ray scattering studies with powder x-ray diffraction and laser-induced fluorescence investigations. Europium, thorium, and uranyl ions were sorbed from aqueous solutions into a chemically functionalized porous silica (termed Diphosil). Aliquots of those samples were heated to a series of temperatures that spanned the pore collapse point. Loading with trivalent europium ions resulted in production of nanophases whose size corresponded to the average number of metal ions per pore. Thorium or uranyl ions resulted in retention of porosity to higher temperature with eventual pore collapse that evidently resulted in formation of nanophases whose size exceeded that determinable under the experimental conditions.