Rapid formation of active, mesoporous, and crystalline TiO2 photocatalysts via a novel microwave hydrothermal process is presented. Crystalline anatase mesoporous nanopowders 100-300 nm in size with worm hole-like pore sizes of 3-5 nm were prepared by a modified sol-gel of titanium tetra-isopropoxide, accelerated by a microwave hydrothermal process. The organic surfactant, tetradecylamine, which is used as a self-assembly micelle in the sol-gel and microwave hydrothermal process, enables to harvest crystallized mesoporous anatase nanoparticles with a high-surface area. Mesoporous worm hole-like and crystalline powders with surface areas of 243-622 m(2)/g are obtained. X-ray diffraction, N-2-adsorption isotherms (Barrett-Joyner-Halenda and Brunauer-Emmet-Teller method), scanning electron microscope, and transmission electron microscope are used to identify the characteristics and morphologies of the powders. It is shown that crystallization by calcination at 400 degrees C/3 h inevitably reduced the surface area, while the microwave hydrothermal process demonstrated a rapid formation of crystalline mesoporous TiO2 nanopowders with a high-surface area and excellent photocatalytic effects.