Technetium-99 (Tc-99) (beta(-)(max): 293.7 keV; t(1/2): 2.1 x 10(5) years) is a byproduct of uranium-235 fission and comprises a large component of radioactive waste. Under aerobic conditions and in a neutral-basic environment, the pertechnetate anion ((TcO4-)-Tc-99) is stable. (TcO4-)-Tc-99 is very soluble, migrates easily through the environment and does not sorb well onto mineral surfaces, soils, or sediments. This study moves forward a new strategy for the reduction of (TcO4-)-Tc-99 and the chemical incorporation of the reduced Tc-99 into a metal oxide material. This strategy employs a single material, a polyoxometalate (POM), alpha(2)-[P2W17O61](10-), that can be photoactivated in the presence of 2-propanol to transfer electrons to (TcO4-)-Tc-99 and incorporate the reduced Tc-99 covalently into the alpha(2)-framework to form the (TcO)-Tc-99-O-V species, (TcO)-Tc-99-O-V(alpha(2)-P2W17O61)(7-). This occurs via the formation of an intermediate species that slowly converts to (TcO)-Tc-99-O-V(alpha(2)-P2W17O61)(7-). Extended X-ray absorption fine structure and X-ray absorption near-edge spectroscopy analysis suggests that the intermediate consists of a Tc-99(IV) alpha(2)-species where the Tc-99 is likely bound to two of the four W-O oxygen atoms in the alpha(2)-[P2W17O61](10-) defect. This intermediate then oxidizes and converts to the (TcO)-Tc-99-O-V(alpha(2)-P2W17O61)(7-) product. The reduction and incorporation of (TcO4-)-Tc-99 was accomplished in a "one pot" reaction using both sunlight and UV irradiation and monitored as a function of time using multinuclear nuclear magnetic resonance and radio thin-layer chromatography. The process was further probed by the "step-wise" generation of reduced alpha(2)-P2W17O6112- through bulk electrolysis followed by the addition of (TcO4-)-Tc-99. The reduction and incorporation of ReO4-, as a nonradioactive surrogate for Tc-99, does not proceed through the intermediate species, and (ReO)-O-V is incorporated quickly into the alpha(2)-[P2W17O61](10-) defect. These observations are consistent with the periodic trends of Tc-99 and Re. Specifically, Tc-99 is more easily reduced compared to Re. In addition to serving as models for metal oxides, POMs may also provide a suitable platform to study the molecular level dynamics and the mechanisms of the reduction and incorporation of Tc-99 into a material.