Advanced SnO₂ nanostructured materials are of great interest for photocatalytic organic pollutants degradation and electrochemical energy storage and conversion. However, they still exhibit unsatisfactory performance because of their limited active sites. To create more efficient architectures, bifunctional hierarchical SnO₂ spheres constructed by extremely thin nanosheet subunits were synthesized through a facile hydrothermal process in ethanol/water medium with subsequent calcination treatment. These SnO₂ nanosheets in the spheres are less than 10 nm thick and consist of amorphous matrices and nanoscaled particles, which show preferential exposure of (001) facets. The photocatalytic and lithium storage properties of the hierarchical SnO₂ spheres were investigated. Compared with that of the commercial SnO₂ powders, the nanosheet-constructed SnO₂ spheres possess more efficient photocatalytic activity for degradation of Rhodamine B and much higher reversible capacity of 765 mAh g⁻¹ even up to 50th cycle and superior stability for lithium storage, which endows them with great potential applications in photocatalysis and lithium-ion anodes.