[en] Highlights: • Atomic layer deposition seeded process coupled with hydrothermal lithiation was created for synthesis of Li₄Ti₅O₁₂/graphene. • TiO₂ nanoislands as seeds were anchored on graphene by ALD, triggering the unique structure of subsequent Li₄Ti₅O₁₂. • Li₄Ti₅O₁₂/graphene as anode of lithium ion capacitors exhibits exceptional electrochemical performances. • The route provides a roadmap for synthesis of Li₄Ti₅O₁₂ based composite and new insights into lithium ion capacitors. High performance composite of nanosized Li₄Ti₅O₁₂ (LTO) and graphene nanosheets was fabricated using a novel atomic layer deposition (ALD) seeded process incorporated with hydrothermal lithiation for the first time. TiO₂ nanoislands as seeds were anchored on graphene by ALD process, triggering the unique structure formation of subsequent LTO. The synergistic effects of nanosized LTO and graphene endow the composite with a short lithium ion diffusion path and efficiently conductive network for electron and ion transport, boosting the excellent reversible capacity, rate capability, and cyclic stability as anode materials for lithium ion capacitors (LICs). The reversible capacity of 120.8 mA h g⁻¹ at an extremely high current rate of 100 C was achieved successfully, and the electrode can be charged/discharged to about 70% of the theoretical capacity of LTO in 25 s. Meanwhile, the composite exhibited excellent cyclic stability of 90% capacity retention at 20 C with nearly 100% Coulombic efficiency after 2500 cycles. The sintering treatment after hydrothermal reaction has significant effects on the crystallinity, defect density, microstructure and electrochemical property of the composite, which is also supported by theoretical calculations. The results provide a versatile roadmap for synthesis of high performance LTO based composite and new insights into LICs.