The practical application of spinel-structured H4Ti5O12(HTO) lithium-ion sieves (LISs) is hampered by their poor adsorption properties and recyclability. Within this research, the surface properties and internal structure of lithium-ion sieve (LIS) materials were modulated by co-doping Fe and Zr metal ions to enhance their adsorption properties. The results show that Fe and Zr have been successfully introduced to the LIS lattice, increasing Li-O bond length of position 8a and O2− content. The synthesized H4Ti4.77Fe0.2Zr0.03O12 (HTFZO-II) LIS was made up of evenly distributed nanosheets layered on top of one another to create an open laminar structure, which possesses a hydrophilic surface (contact angle: 17.8°), a high surface area (95.89 m2/g), and hierarchical porous structure. Compared with the undoped HTO, the HTFZO-II LISs enjoy a high capacity for Li+ adsorption (28.72 mg/g), a strong cycling stability (Ti4+ dissolving loss: 0.12 %), and a fast reaching of the equilibrium in adsorption (adsorption equilibrium: 4 h). Theoretical calculation of DFT shows that Li(H2O)4+ on HTFZO-II and HTO dehydration were partially dehydrated into Li(H2O)+. The energy required for the dehydration of Li(H2O)4+ on HTFZO-II is lower than that on undoped HTO, indicating that metal ion doping modification was beneficial for the dehydration of hydrated lithium ions on the adsorbent surface, thereby accelerating the exchange reaction between H+ and dehydrated Li+ ions. This study reveals the key role of the synergistic effect of multi-element co-doping in enhancing the adsorption performance and structural stability of LISs.