To determine the lattice constant variation with burn-up and the oxidation behaviour at high temperatures, simulated UO 2 -spent fuels with burn-ups up to 200 GWdtM −1 were prepared by cold pressing and sintering and characterised by X-ray diffraction analysis and thermogravimetry. The fcc-lattice parameter of the sintered samples determined at room temperature, showed a continuous decrease with the simulated burn-up. During oxidation the conversion of the simulated fuels to the (U,FP) 4 O 9 and (U,FP) 3 O 8 -type phases was strongly delayed when the simulated burn-up exceeded 80 GWdtM −1 . Also, at high burn-ups (>100 GWdtM −1 ), large fractions of the (U,FP) 4 O 9 -type phase remained untransformed to (U,FP) 3 O 8 after prolonged exposure to air at 950–1000°C. This suggests a marked widening of the (U,FP) 4 O 9 -phase field when the amount of substituted uranium atoms exceeds values of about 8%.