Periodic array of titanium dioxide (TiO2) microprojections was fabricated in aqueous solutions using poly(methylmethacrylate) (PMMA) films with ordered microcavities as a mold. The periodic microprojections consisting of crystalline TiO2 exquisitely transcribed the architecture of the mold without deformation or shrinkage. This biomimetic route including preferable nucleation on the specific organic surface and subsequent growth of the crystalline phase at a low temperature is applicable to construct three-dimensional periodic architectures for photonic structures of various metal oxides.