A hierarchical, nanoporous TiO2 structure is successfully prepared by a simple in situ hydrolysis method. Used as an anode material, it achieves a sustained high lithium storage performance especially at high charge/discharge rates due to its substantially high surface area. The material shows two different major storage modes: a) bulk insertion, and b) pseudo‐capacitive interfacial storage, which is responsible for 64% of the total capacity. In order to kinetically emphasize the interfacial storage even further, we cycle the material directly at high rates, giving 302 mA h g−1 and 200 mA h g−1 of fully reversible discharge capacity at charge/discharge rates of 1 C and 5 C with very high cycle stability. We propose an overall view on the different Li insertion mechanisms of the high‐surface‐area nanoporous TiO2 and emphasize the importance of interfacial storage for electrode applications in Li‐ion batteries.