High-level waste (HLW) is a waste associated with the dissolution of spent nuclear fuel for the recovery of weapons-grade material. It is the priority problem for the U.S. Department of Energy's Environmental Management Program. Current HLW treatment processes at the Savannah River Site (Aiken, SC) include the use of monosodium titanate (MST, with a similar stoichiometry to NaTi2O5 x xH2O) to concentrate strontium (Sr) and actinides. The high affinity of MST for Sr and actinides in HLW solutions rich in Na+ is poorly understood. Mechanistic information about the nature of radionuclide uptake will provide insight about MST treatment reliability. Our study characterized the morphology of MST and the chemistry of sorbed Sr2+ and uranium [U(VI)] as uranyl ion, UO2(2+), on MST, which were added (individually) from stock solutions of Sr and 238U(VI) with spectroscopic and transmission electron microscopic techniques. The local structure of sorbed U varied with loading, but the local structure of Sr did not vary with loading. Sorbed Sr exhibited specific adsorption as partially hydrated species whereas sorbed U exhibited specific adsorption as monomeric and dimeric U(VI)-carbonate complexes. Sorption proved site specific. These differences in site specificity and sorption mechanism may account forthe difficulties associated with predicting Sr and U loading and removal kinetics using MST.