This paper describes a surfactant-assisted hydrothermal reduction pathway toward various kinds of antimony and bismuth three-dimensional superstructures, containing hollow spheres composed of nanostrips, peony-like architecture, radial sub-micrometer rod bundles, and a shale-like pattern. These three-dimensional superstructures were obtained through the reduction of SbCl3 or Bi(NO3)3·5H2O by aluminum powder in different emulsion systems at 120°C. The formation mechanism for Sb three-dimensional superstructures has been formally proposed. Some influencing factors on the morphology of the final products have also been discussed. We expect this convenient method can be extended to prepare three-dimensional superstructures of other inorganic materials, which have similar layered structures to Sb and Bi.