Lithium-based ceramics exhibit good thermophysical properties, have low activation and chemical activity, and also release tritium well. These characteristics make lithium ceramics the best candidates for use as a functional material for a solid breeder blanket. To date, the most accurate understanding of the processes of tritium and helium production and release occurring in the breeder blanket materials can only be obtained from the results of reactor experiments. On the other hand, many important parameters can only be estimated in post-irradiation experiments (PIE). This paper describes studies of tritium and helium release in post-irradiation experiments (PIE) on the thermal desorption from ceramic pebbles Li2TiO3 + 5mol% TiO2 (with 96% enrichment on lithium-6 isotope), irradiated in the WWR-K reactor for 223 days. In PIE a peak of helium release was recorded for each sample in the temperature range of 1300–1500 K. An assumption was made in the paper to explain the nature of this helium release peaks from lithium ceramic pebbles.