TiO2-based photocatalysis has been considered to be one of the most promising avenues for environmental remediation including water purification. However, several technical issues such as the limited surface area of bulk TiO2, the large band gap of TiO2, and rapid charge recombination still limit the practical application of TiO2 photocatalysts. Therefore, here we focus on two structural design strategies: (i) monolithic three-dimensional (3D) nanostructuring, and (ii) heterostructuring with graphitic carbon nanomaterials. A monolithic 3D nanostructure enables maximal surface area in a given volume and efficient reuse of the photocatalyst without recollection. Heterostructuring with carbon nanomaterials helps achieve maximal utilization of the solar spectrum and charge separation and provides efficient TiO2 photocatalysts. In this review, recent progress on TiO2 photocatalysts toward the abovementioned strategies will be summarized. Further discussion and direction will provide insights into the rational design of highly efficient TiO2 photocatalysts, and help develop advanced photocatalyst models.