AbstractThe vapor pressures and work function changes of Li4SiO4, Li2ZrO3, Li2TiO3, as well as Li2O at elevated temperatures were measured to investigate their thermochemical behavior. Application of two independent experimental techniques made it possible to understand such behavior from both macroscopic and microscopic standpoints. The experimentally obtained results of vapor pressures and work function changes were closely related to each other, indicating some relevance between macroscopic and microscopic behaviors of hydrogen at the surface of ceramic breeders.