Micrometer-scaled hierarchical tubular structures of CuS assembled by nanoflake-built microsphereswere first synthesized in high yield via a one-pot intermediate crystal templating process without surfactant or added templates, in which the intermediate complex Cu-3(TAA)(3)Cl-3 formed in situand subsequently served as a self-sacrificed template. Whereas the intermediate complex and final hierarchical structures were well characterized, the formation mechanism was preliminarily studied based on X-ray diffraction (XRD) studies and scanning electron microscopy (SEM) observations byarresting the growth at a series of intermediate stages in the formation of the hierarchical tubularstructures. The benefits for the as-obtained nanostructures arise from their ultrahigh Brunauer-Emmett-Teller (BET) value and the potential capacity advantage for the catalyst industry and hydrogen storage.