Abstract The practical application of spinel‐type lithium titanate Li 4 Ti 5 O 12 (LTO) lithium‐ion batteries is hindered by its poor conductivity and relatively low capacity. To address these issues, an LTO/reduced graphene oxide (rGO)/SnO 2 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 SnO 2 to LTO increases the overall conductivity, improves the structure stability, and increases Li‐ion diffusion speed.