AbstractThe practical application of spinel‐type lithium titanate Li₄Ti₅O₁₂ (LTO) lithium‐ion batteries is hindered by its poor conductivity and relatively low capacity. To address these issues, an LTO/reduced graphene oxide (rGO)/SnO₂ is synthesized via an in situ electrostatic self‐assembly and hydrothermal reduction process. Density function theory (DFT) simulations are conducted to understand the geometrical structures of these composites and the energy storage mechanisms. The DFT results confirm that the introduction of rGO and SnO₂ to LTO increases the overall conductivity, improves the structure stability, and increases Li‐ion diffusion speed.