Materials with intricate nanostructures display fascinating properties, which have inspired extensive research on the synthesis of materials with controlled structures. In this study, we investigated the properties of superstructures of TiO2 to understand the inter-relationship between structural ordering and photocatalytic performance. The nanoplate anatase TiO2 mesocrystals were chosen as the typical investigation objects, which were newly synthesized by a topotactic structural transformation. The TiO2 mesocrystals displayed the superstructure of crystallographically ordered alignment of anatase TiO2 nanocrystals with high surface area and large high-energy surface {001} planes exposed. The photoconductive atomic force microscopy and time-resolved diffuse reflectance spectroscopy were utilized to determine the charge transport properties of TiO2 mesocrystals, and their features were highlighted by a comparison with reference TiO2 samples, for example, anatase TiO2 nanocrystals with similar surface area and single crystal structure. Consequently, it was found for the first time that such a superstructure of TiO2 could largely enhance charge separation and had remarkably long-lived charges, thereby exhibiting greatly increased photoconductivity and photocatalytic activity.