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Abstract: Out-of-pile tritium release experiments under different water uptake contents and purge gas chemistry were performed on Li4SiO4. Water measurement was performed on samples under different experimental procedures. It was found that water was adsorbed on the sample during its transferring and storage process. A strong dependence of tritium release behavior on water uptake was determined. By doping H2 in the sweep gas, the formation of water in orthosilicate was observed in addition to the isotope exchange reaction with H2 gas. Thermal desorption peaks of the water formation reaction and H2 isotope exchange reaction appeared at 668°C and 463°C, respectively, at ramping rate of 5°C/min. [Copyright &y& Elsevier]