The present paper reports a simple route to fabricate high surface area anatase TiO₂ mesoflowers from electrospun TiO₂–SiO₂ composite nanostructures. Electrospun fiber- and rice-shaped TiO₂–SiO₂ composite nanostructures upon treatment with concentrated alkali (NaOH) under hydrothermal conditions (180 °C) result in chemical transformation of the TiO₂ and in situ etching of SiO₂ to give sodium titanates. The sodium titanate upon acidification followed by a low temperature sintering (180 °C) results in 3D TiO₂ mesoflowers. The material is found to be superior to the commercial P-25 in photocatalysis.