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.