Three-dimensionally ordered macro-/mesoporous (3DOM/m) TiO2 monoliths were fabricated by a dual-templating synthesis approach employing a combination of both colloidal crystal templating (hard-templating) and surfactant templating (soft-templating) techniques. Titania precursor, consisting of amphiphilic triblock copolymer Pluronic P123 as a mesopore-structure-directing agent and titanium tetraisopropoxide as a titanium source, was infiltrated into the void spaces of the poly(methyl methacrylate) (PMMA) colloidal crystal monolith. Subsequent thermal treatment produced 3DOM/m TiO2 monolith. The macropore walls of the prepared 3DOM/m TiO2 exhibit a well-defined mesoporous structure with narrow pore size distribution, and the mesopore walls are composed of nanocrystalline anatase TiO2. The material also shows a high surface area (171 m2/g), and large pore volume (0.402 cm3/g).