In order to efficiently grasp the tritium behavior in advanced core-shell breeding materials, this study adopts a route of injecting tritium out-of-pile to deal with the problems of fewer platforms, long periods, and high costs for traditional neutron irradiation-tritium release experiments. Here, tritium adsorption and desorption experiments were carried out with Li4TiO4-Li2TiO3 core-shell breeding materials before and after long-term heating up to 30 days. The purpose is to study whether the structural changes caused by long-term heating will affect the adsorption and desorption behavior of tritium on the sample surface. The results show that the lack of chemically adsorbed water caused by long-term heating will significantly weaken the tritium adsorption capacity of the sample, but will not affect the desorption behavior of Ar, 1%H2+Ar and water vapor on tritium, so all samples show a very low tritium retention.