Single-crystal-like TiO2 hierarchical spheres, which own the advantages of both high energy facets and big surface area, were successfully synthesized via a biomolecule-inspire method. Exposed facets of these TiO2 samples were custom-designed by controlling the additive amount of L-lysine. The formation mechanism was preliminary studied. Single-crystal-like TiO2 seems to grow through a facile oriented growth mechanism with the help of the capping synergetic effect of SO42- and lysine. Only appropriate ratios of lysine to SO42- can help the formation of single-crystal-like anatase TiO2 with exposed {1 0 1}, {1 1 1} planes. Both high surface area and the exposure of peculiar planes can enhance photocatalytic activity. (C) 2015 Elsevier B.V. All rights reserved.