Well controlled nanosheets-based hierarchical microspheres (NSHMS) of pure covellite phase CuS were synthesized using a facile PVP assisted solvothermal process. The reaction conditions were optimized using various amounts of PVP to develop unique hierarchical structured hollow microspheres. CuS hollow structures have a bandgap of ~1.97 eV. These mesoporous structures exhibit excellent photocatalytic activity in degradation of organic dyes (Methylene Blue) under natural light in comparison to other structures of copper sulphide. These photocatalysts show extraordinary reusability with over 96.5% degradation of organic dye after 6th cycle. A "bottom-up" assembly was successfully developed to synthesize hollow microspheres with unique and well defined architectures at large scale, which offer a good opportunity to understand the fundamental significance of unusual and complex hierarchical structures for their potential applications. This journal is the Partner Organisations 2014.