The interactions between tellurium and organic material during a nuclear reactor accident are critical to source term estimations because of the possible formation of volatile species. Reactions taking place in the containment sump are of interest since these can lead to re-volatilization and increase the fission product source term. This paper presents results from experiments investigating the interaction of tellurium dioxide with three paint solvents—texanol ester, methyl isobutyl ketone, and toluene—under containment sump conditions. The experiments were performed by irradiating a mixed solution of tellurium dioxide and paint solvents at a dose rate of 4 kGy/h up to 300 kGy. The resulting samples were analyzed for tellurium concentration and speciation. Tellurium(IV) was found to reduce to metallic tellurium under irradiation when paint solvents were present. More importantly, several volatile organic tellurides were identified in the irradiated samples, which suggests that tellurium can form volatile species in sump conditions when in contact with dissolved paint solvents. This paper provides novel evidence of organic telluride formation in the sump and raises further interest in tellurium chemistry during a severe nuclear reactor accident.