A facile hydrothermal approach has been developed to prepare defective TiO2-x nanocrystals using Ti(III)-salt as a precursor and L-ascorbic acid as reductant and structure direction agent. The prepared TiO2-x nanocrystals are composed of a highly crystallized TiO2 core and a disordered TiO2-x outer layer, possessing high surface area, controlled oxygen vacancy concentration and tunable bandgap via simply adjusting the amount of added L-ascorbic acid. The defective TiO2-x shows high photocatalytic efficiency in methylene blue and phenol degradation as well as in hydrogen evolution under visible light, underlining the significance of the present strategy for structural and bandgap manipulation in TiO2-based photocatalysis.