A versatile synthetic method which is based on a solvothermal technique for the fabrication of highly crystalline TiO2 nanocrystals (NC) exhibiting different shapes such as rhombic, truncated rhombic, spherical, dog-bone, truncated, and elongated rhombic is reported. The dominant features of the present approach are first the use of water vapor as hydrolysis agent to accelerate the reaction, and second, the use of both oleic acid (OA) and oleylamine (OM) as two distinct capping surfactants having different binding strengths for the control of the growth of the TiO2 nanoparticles. It is shown that the presence of an appropriate amount of water vapor along with the desired OA/OM molar ratio plays a crucial role in controlling size and shape of TiO2 NCs. Moreover, it is also established that the thus-obtained TiO2 NCs are excellent support for the synthesis of composite metal/TiO2 photocatalysts in which metal clusters are uniformly deposited on the surface of each individual TiO2 NC. (C) 2011 Canadian Society for Chemical Engineering