The controllable synthesis of two novel types of BiVO4 mesocrystals, with flower-like and dendrite morphology, has been successfully realized via a facile aqueous strategy. Without any additive, the primary building units perfectly aligned in three-dimension and built up well-defined mesocrystals with sharp facets and edges. The formation mechanism was further investigated, and new growth models for the mesocrystals were observed. It was found that that the pH value and reaction temperature had great influences on the formation of these unique mesocrystals. The present study not only opens new avenues for rationally designing various kinds of inorganic materials with ideal hierarchy and controllable length scale but also offers a good opportunity to understand the formation process of these unique crystalline superstructures.
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