Uniform bismuth selenide hollow nanospheres were synthesized on a large scale in a mixed solvent of ethylene glycol (EG) and oleic acid (OA). The diameter of the Bi
2Se
3 hollow nanospheres is about 600 nm and the thickness of the shell is about 40 nm. The shape evolution of Bi
2Se
3 nanostructures with different volume ratios of EG and OA was also observed: nanoflakes in EG solution, hollow nanospheres as
of 2/3, and finally flower-like nanostructures in OA solution.