Unique hierarchical cancellous-bone-like microstructures, composed of a TiO2 nanonet (nanofiber network), have been fabricated by a facile and cost-effective process that combines the electrospinning technique with the template method. The branching three-dimensional network trabeculae that form rod- and plate-shaped scaffolds have thickness of approximately 0.5 to 2.5 mu m and consist of TiO2 nanonet. The nanonet exhibits an anatase crystalline structure and a maximum Brunauer-Emmett-Teller specific surface area of 225.9 m(2)/g. This hierarchical three-dimensional nano/micro porous network material creates numerous interconnected pores with a high surface area that enhances the overall efficiency of the network due to an increase in the accessible surface area, which increases the contact with the reaction media. (C) 2012 Elsevier B.V. All rights reserved.