Controlled crystal growth determines the shape, size, and exposed facets of a crystal, which usually has different surface physicochemical properties. Herein we report the size and facet control synthesis of anatase TiO2 nanocrystals (NCs). The exposed facets are found to play a crucial role in the photocatalytic activity of TiO2 NCs. This is due to the known preferential flow of photogenerated carriers to the specific facets. Although, in recent years, the main focus has been on increasing the surface area of high-energy exposed facets such as {001} and {100} to improve the photocatalytic activity, here we demonstrate that the presence of both the high-energy {001} oxidative and low-energy {101} reductive facets in an optimum ratio is necessary to reduce the charge recombination and thereby enhance photocatalytic activity of TiO2 NCs.