Lithium oxide is a potential solid-state blanket material for fusion applications. Equilibrium water vapour pressure in the system Li2O-H2O including dehydration LiOH H2O and dissociation LiOH were studied in a temperature range 70–160 and 270–440°C respectively. The kinetics of LiOH dissociation was studied in a range 390–450°C by Mak Ben quartz spring balance and in a range 450–600°C by volumetric method collecting hydrogen after chemical decomposition of water on hot metal. Kinetics of tritium oxide release from neutron irradiated lithium oxide with initial concentration 1,11 109 and 3,33 109 Bq/g was studied in vacuum 1,333 Pa in the range 280–450°C. The initial and final stages of the process are characterized by activation energies of 83,5 and 54,4 kJ/mol, respectively. Taking into account the formation of OT groups into inorganic compound under irradiation a mechanism of water and tritium oxide formation and recovery from solid phase is a chemical recombination reaction (polycondensation) which brings to the formation of H2O or HTO and inorganic polymer (sintering).