An investigation into the influence of 3D superstructures of layered titanate on the electrochemical properties and Li-insertion performance was carried out. The electrode surfaces after cycling performance were also characterized by FE-SEM and XRD. Titanate samples that contain interconnected “house-of-cards”-type mesostructured nanoflakes show broad and distinct CV peaks, revealing a sluggish process and great capacitive behavior. These materials are more beneficial to battery performance than diamond-shaped anatase particles. The charge-discharge voltage profiles of the hierarchical titanate gradually decay without any potential plateau. Based on the specific capacity, rate capability and cycling testing, the novel macrochannel architecture assembled by “house-of-cards”-like walls efficiently facilitates Li+ insertion/extraction and possesses better electronic conductivity than other geometries.