The paper shows the usage of destructive assay data from PWR fuel samples for the validation of the NFCSS burnup system developed by the IAEA. The results of radiochemical measurements of spent fuel isotopic composition were compared with the results of numerical modelling. In total, 254 samples from 15 PWRs, incorporated in the SFCOMPO database, were applied in the validation study. The paper shows the trends observed in the calculated-to-experimental ratios for eight major actinides and six minor actinides present in spent nuclear fuel. The data were quantified and analysed considering the enrichment, burnup and origin. The obtained results were compared with other studies on burnup validation using different numerical tools. In general, the results of numerical modelling for major actinides show rather good consistency with radiochemical measurements, while the results for minor actinides are less accurate.