Nanoplate-based copper sulfide (CuS) hierarchical hollow spheres have been successfully synthesized using the spontaneous oil droplets as the templates in a two-phase system. In this approach, the poorly crystallized CuS hollow spheres with an average diameter of about 1 mu m can be obtained at a low temperature and then grow into the hierarchical CuS hollow spheres composed of nanoplates through a recrystallization growth process at a higher temperature. Furthermore, the growth process of the nanoplates of the hierarchical CuS hollow spheres can be controlled by changing the ripening time. In addition, the photocatalytic activity of the hierarchical CuS hollow spheres has been evaluated by the degradation of methylene blue solution in the presence of hydrogen peroxide under natural light, showing that the as-prepared hierarchical CuS hollow spheres exhibit high photocatalytic activity for the degradation of methylene blue (MB). (c) 2012 Elsevier B.V. All rights reserved.