The phenomena of Schottky barrier creation in RbAg4I5are studied. Luminescence with high spatial resolution is used as a tool for investigation of the process on the blocking electrode-solid electrolyte boundary. The profile of the distribution of electronic centers near the contact region is measured. The presence of electrons and ions in the depletion region at the interface between the RbAg4I5and the graphite electrode is established and interpreted within the framework of the modified Schottky model. The kinetics of the creation of Schottky barriers is measured and described by taking into account the presence of self-trapped electrons and mobile silver ions in RbAg4I5. It is shown that the small value of the self-trapped electron diffusion coefficient (Dst≃ 1 × 10−8cm2/sec) limit the kinetics of the process of creation of Schottky barriers.