In the event of a severe nuclear accident, one major concern is the release of radioactive material into the environment causing potential exposure of the general public to radiation. Among the volatile radionuclides are a range of tellurium isotopes. Due to the radioactivity and the volatility of tellurium, it has to be taken into account when assessing the overall effects of an accident. The interest in tellurium is not limited only to its release but also to the fact that some tellurium isotopes decay to iodine, and thus affect the iodine release behavior. The release and transport behavior of tellurium has been investigated over the past decades, however, the aqueous chemistry of tellurium in the complex containment sump system is still unclear. This study presents the behavior of tellurium dioxide in simplified containment sump conditions in relation to dissolution, redox reactions, and interactions with water radiolysis products. The results indicate that radiolysis products have a significant effect on tellurium chemistry in both a reducing and oxidizing manner depending on the solution composition. The redox reactions also affect the solubility of tellurium. The results show that the current information used to assess tellurium source term needs to be reevaluated for both severe accident management and for code validation purposes.