During the past decades, fusion reactor fuels such as deuterium and tritium have been extensively investigated due to increasing interest in nuclear fusion energy. Tritium, which is scarce in nature, needs to be fabricated by tritium breeder materials. Among the commonly investigated tritium breeder materials, lithium titanate (Li2TiO3) is recognized as one of the most promising solid tritium breeder materials because of its considerable lithium (Li) atomic density, low activation, excellent chemical stability, and low-temperature tritium release performance. This paper aims to provide a systematic review of the current progress in Li2TiO3 preparation methods as well as the high Li density, tritium release performance, irradiation behavior, and modification technologies of Li2TiO3 pebbles. Li2TiO3 can be synthesized by strategies such as solid-state, sol–gel, hydrothermal, solution combustion synthesis, and co-precipitation methods. Among them, the hydrothermal method is promising due to its simplicity and low cost. Many researchers have begun to focus on composite ceramic pebbles to further improve tritium breeder performance. This will provide a new direction for the future development of Li2TiO3 pebbles. The present review concludes with a summary of the preparation methods currently under development and offers an outlook of future opportunities, which will inspire more in-depth investigation and promote the practical application of Li2TiO3 in this field.