Hollow spheres of elemental antimony (Sb) with good crystallinity, high contrast and thin wall were prepared in the solutions of poly(ethylene glycol) (PEG) and oleic acid(OA) associations at the refluxed temperature. The complexes of Sb3+ with tartaric acid were used as precursors, which can avoid the hydrolysis of SbCl3 and the resulting impurity of products. The average diameter and thickness of the as-prepared hollow sphere are about 300 nm and less than 20 nm, respectively. The formation of hollow spheres depends on the template function of PEG and OA associations, which can be confirmed through the theoretical analysis and results of control experiments. The specific surface area reaches 34.669 m2/g.