In this study, the precursor γ-Li2TiO3 was synthesized utilising the Kirkendall effect, which entailed mixing titanium and lithium sources at the nano-scale and calcining the resulting mixture at a low temperature (923 K). The X-ray diffraction data demonstrated that the crystal cell parameter values of the axial lengths a = b = c are each 8.372 Å and that the axis angles α = β = γ are each 90°, which align with γ-Li2TiO3 parameters. In addition, the characteristic lattice stripes of γ-Li2TiO3 appeared clearly in its transmission electron microscopy images. The chemical compound γ-H2TiO3 was derived from the precursor γ-Li2TiO3 through pickling. Because of the cavity effect of the lithium-ion sieve used, only H+ and Li+ could enter and exit the sieve freely, resulting in the selective adsorption of Li+. The Li+ adsorption capacity of γ-H2TiO3 was high (74.85 mg g−1) with good selectivity. The adsorption behaviour of Li+ followed the Langmuir monolayer molecular adsorption behaviour and could be determined using the chemisorption kinetic model. Moreover, γ-H2TiO3 exhibited superior adsorption capacity than layered titanium-ion sieves and the cyclic adsorption of γ-H2TiO3 was more efficient than that of layered titanium-ion sieves. Thus γ-H2TiO3 can be used in industrial applications involving lithium extraction.