Understanding polonium evaporation from lead-bismuth eutectic (LBE) is required for the design of nuclear installations that use liquid LBE as coolant or spallation target. In the present study we measured the time-dependent release of polonium from LBE samples in Ar/5 %H2 and Ar between room temperature and 500 C. Our experiments revealed that the majority of polonium in the samples evaporated according to established temperature correlations for the Henry constant of polonium in LBE. However a small fraction of polonium in the LBE behaved differently, causing a relatively large but transient polonium release at the start of evaporation experiments. We showed that this volatile fraction of polonium was located near the sample surface and was formed after prolonged exposure of the samples to air at room temperature. We speculate that the peculiar evaporation behavior of this surface polonium is caused by enrichment and association with an oxide layer.