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Then, we describe the synthetic strategies of nanoporous TiO2 and titanate spheres using various HTCS as self-templates. Here, the focus lies on the interactions between TiO2 nanobuilding blocks with precursors or media at the solid/liquid and solid/solid interfaces, the concurrent phase transitions, and the microstructural and morphological evolutions. Selective formation of crystal phase and internal structures (e.g., solid, hollow, core-shell, yolk-shell) are discussed by manipulating the crystallization kinetics. To further elucidat