The volatilization of technetium in the course of high-level waste vitrification may be considerable, depending on process variations. A series of experiments has been performed in order to gain more insight into the vaporization behavior of Tc during HLLW vitrification. No losses have been observed during chemical denitration or drying of the solutions on a drum drier at moderate temperatures. However, substantial volatilization (40–60 %) occurred during high temperature processing which applied either liquid feeding or feeding as a dehydrated product into the glass melter. Details of parameters investigated are described, and consequences for technical process application are discussed.