Efforts are underway at Oak Ridge National Laboratory to improve the nuclide inventory validation basis for spent nuclear fuel at high burnups. Recently conducted radiochemical assay experiments provided new measurement data for nine samples of fuel irradiated in a pressurized water reactor, with estimated sample burnups in the 30 to 70 GWd/t range. This type of destructive assay data is essential for validating computational methods, tools, and nuclear data applied in nuclear safety analyses and for improving our understanding of the bias and uncertainty in code predictions. The measurement data include key actinides and fission products that span a gamut of needs and interests for nuclear science and engineering applications in criticality safety, reactor physics, nuclide inventory, decay heat, and radiation shielding. The SCALE 6.3 code system with ENDF/B-VII.1 cross-section libraries was used to simulate the irradiation histories of the measured fuel samples. The calculated nuclide concentrations are compared to corresponding measurement data. The significance of the comparisons is discussed, emphasizing how the addition of the new measurement data fills gaps in the validation basis at high burnups and contributes to the decrease in bias and uncertainty for predicted nuclide concentrations. The discussion addresses the effect of the sample burnup used in the simulation—which is based on reactor operator records or on calibration to measured data for burnup indicator fission products—on the validation results.