Lithium orthosilicate (Li4SiO4) pebbles are considered as the candidate tritium breeders of Chinese helium cooled solid breeder test blanket module (CH HCSB TBM). The post-irradiation annealing experiments of lithium orthosilicate ceramic pebbles, made by freezen-sintering process, have been performed in CAEP. The samples were purged with 100mL/min mixed gas of He +1% H2, heated at a constant rate of 5K•min-1 in a reactor tube. The results showed that tritium was released mainly as tritium gas (HT+T2), the proportion was about 70% except that in free tritium released out before annealing, and there were two tritium release peaks from 400℃~700℃. On the other hand, percentage of tritiated water (HTO+T2O) was less than 20%, and released at lower temperature region of 300℃~500℃. Tritium remained in the pebbles was less than 1% after 800℃ in annealing experiments, so Li4SiO4 pebbles made by freezen-sintering process have favorable tritium release performance, and have potential application in fusion reactor solid blanket system.