The electrolytic reduction process in pyroprocessing of used fuel requires that fuel fragments be pre-treated to remove cesium and iodine. The effect of high temperatures and fuel fragment size on release of cesium was investigated over 10 h at a temperature of 1300–1400 °C for fuel fragments with an O/U ratio of 2.2. Re-fragmentation of the original fragments was observed as changes in cesium release count rates as fuel was heated from 484 to 1329 °C. The release of cesium is highly dependent on the size of fuel fragments and most of the cesium is released as the temperature is held at the maximum target value.