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Rare-earth based A 2 B 2 O 7 compounds have been considered as potential host materials for nuclear waste due to their exceptional chemical, physical, capability of accommodating high concentration of actinides at both A- and B-sites, negligible leaching, tendency to form antisite defects, and radiation stabilities. In this work, La 2 Hf 2 O 7 (LHO) and Gd 2 Hf 2 O 7 (GHO) nanoparticles (NPs) were chosen as the RE-based hafnates to study the structural changes and the formation of different U molecular structures upon doping (or alloying) at high concentration (up to 30 mol %) using a combined coprecipitation and molten-salt synthesis. These compounds form similar crystal structures, i.e., ordered pyrochlore (LHO) and disordered fluorite (GHO), but are expected to show different phase transformations at high U doping concentration. X-ray diffraction (XRD) and Rietveld refinement results show that the LHO:U NPs have high structural stability, whereas the GHO:U NPs exhibit a highly disordered structure at high U concentration. Alternatively, the vibrational spectra show an increasingly random oxygen distribution with U doping, driving the LHO:U NPs to the disordered fluorite phase. X-ray spectroscopy indicates that U is stabilized as different U 6+ species in both LHO and GHO hosts, resulting in the formation of oxygen vacancies stemming from the U local coordination and different phase transformation. Interestingly, the disordered fluorite phase has been reported to have increased radiation tolerance, suggesting multiple benefits associated with the LHO host. These results demonstrate the importance of the structural and chemical effect of actinide dopants on similar host matrices which are important for the development of RE-based hafnates for nuclear waste hosts, sensors, thermal barrier coatings, and scintillator applications.