Although solution-based synthesis is the most powerful and economic method to create nanostructured anatase TiO2, under those synthesis conditions the {101} facets are the most thermodynamically stable, making it difficult to create anatase nanomaterials with a large percentage of high-energy {001} or {010} facets exposed. Here, we report a facile nonaqueous synthetic route to prepare anatase nanosheets with exposed {001} facets and high-quality rhombic-shaped anatase nanocrystals with a large percentage of exposed {010} facets. Including adscititious water in the nonaqueous synthesis and eliminating the use of carboxylic acid type capping agents are the two keys to integrating the structural diversity from aqueous systems into large-quantity synthesis in nonaqueous systems. The nanostructured TiO2 that we prepared exhibits conspicuous activity in the photocatalytic degradation of organic contaminants.