The design of one-dimensional titania with tunable structural hierarchy holds exciting implications for applications such as optoelectronics, sensing and catalysis. Here, we report a general precursor strategy for one-dimensional titania with surface nanoprotrusion and tunable hierarchical structures realized via a titanate route using electrospun titania fibers as precursors. One-dimensional hierarchical hollow titanate (1D-HHT) was first fabricated under mild alkaline hydrothermal conditions from electrospun amorphous TiO₂precursors. The time-dependent evolution of 1D-HHT has been investigated in detail. The concerted effect of alkaline etching and Ostwald ripening is responsible for the surface nanoprotrusion and modulation of structural hierarchy. Anatase TiO₂with the same hierarchical structures can be obtained using controlled calcination. The as-fabricated one-dimensional titania with varying levels of structural hierarchy exhibits about 1.3-1.5 times higher power conversion efficiency than commercial P25 as a photoanode material for dye-sensitized solar cells (DSSCs). The current work may be extended for more functional TiO₂-based materials with tunable structural hierarchy and could widen the application range of electrospinning technology for one-dimensional hierarchical structures.