In this work, we describe a kinetically controlled crystallization process assisted by an oriented attachment (OA) mechanism based on a nonaqueous sol-gel synthetic method (specifically, the reaction of titanium(IV) chloride (TiCl(4)) with n-octanol) to prepare re-crystallized anatase TiO(2) mesocrystals (single crystal). The kinetics study revealed a multi-step and hierarchical process controlled by OA, and a high resolution transmission electron microscopy (HRTEM) analysis clearly shows that the synthesized mesocrystal presents a truncated bipyramidal Wulff shape, indicating that its surface is dominated by {101} facets. This shape is developed during the recrystallization step. The material developed here displayed superior photocatalytic activity under visible light irradiation compared to TiO(2)-P25 as a benchmarking.