TiO2 hollow spheres with porous crystalline shells are fabricated by hydrothermal treatment, and possess uniform and highly crystallized morphology, exhibit excellent electrochemical performance and high photocatalytic activity, display high specific capacity. Display omitted •TiO2 hollow spheres with porous crystalline shells are fabricated by hydrothermal treatment.•The TiO2 hollow spheres possess uniform and highly crystallized morphology as well as large surface area.•The TiO2 hollow sphere material exhibits excellent electrochemical performance and high photocatalytic activity. TiO2 hollow spheres with porous crystalline shells were synthesised by hydrothermal treatment. The as-prepared samples possessed uniform and highly crystallized morphology have exhibited excellent electrochemical performance (high specific capacities of 223 mAh g−1 at 0.5 C after 100 cycles, and 129 mAh g−1 at 5 C after 100 cycles) and high photocatalytic activity, which indicating that TiO2 hollow nanocrystals have promising values in photocatalysis and advanced Li-ion batteries. The improvement of electrochemical performance and excellent photocatalytic activity is attributed to large surface areas, small crystallite size and unique hollow sphere nanostructure. The process in this paper provides a general route to synthesis hollow nanostructures composites. The as-prepared TiO2 hollow sphere nanostructures are also of great interests in catalysis, lithium-ion batteries, separation technology and nanotechnology.