A new approach for the fabrication of oriented TiO₂/glass nanoflake arrays has been developed. The ceramic nanoflake array was formed on a glass substrate via a simple, low temperature, and one-step hydrothermally induced phase separation approach without using any templates or additives. The factors affecting the formation of ceramic nanoflakes were examined by various characterization techniques. The results showed that the leaching of the soluble phase from the glass surface through hydrothermal processes resulted in oriented uniform ceramic nanoflake arrays. Electron microscope observations revealed that the nanoflakes formed a continuous porous three-dimensional-network array with a large surface-to-volume ratio. In addition, an anatase TiO₂ film was successfully coated onto the nanoflake array by the sol−gel method. The TiO₂/glass nanoflake array exhibited high activity for the photocatalytic degradation of acetone and for photoinduced hydrophilic conversion. Such enhancements were attributed to the beneficial effects of the new continuous porous three-dimensional-interconnected nanoflake network and its surface geometrical nanostructure. The present approach provides a convenient route to modify a photocatalytic coating with a porous nano-architectured substrate. This opens extensive new opportunities in the design of semiconductor/ceramic nanostructural array thin films with unusual properties for future optical and electronic applications. Copyright © 2005 American Chemical Society.