The three-dimensional nanostructured SiO2-based microshells of diatoms have been converted into nanocrystalline BaTiO3 via a series of shape-preserving reactions. The microshells, obtained as diatomaceous earth, were first exposed to a surfactant-induced dissolution/reprecipitation process [C.E. Fowler, et al., Chem. Phys. Lett.398, 414 (2004)] to enhance the microshell surface area, without altering the microshell shape. The SiO2 microshells were then converted into anatase TiO2 replicas via reaction with TiF4 gas and then humid oxygen. Hydrothermal reaction with a barium hydroxide-bearing solution then yielded three-dimensional nanocrystalline microshell replicas composed of BaTiO3. The enhanced surface area of the surfactant-treated microshells resulted in faster conversion into phase-pure BaTiO3 at 100 °C.