Visible-light-active a-sulfur spheres with hierarchical nano structures were fabricated by simple solution-phase synthesis with PVP as the template for enhanced photocatalytic ability. The alpha-sulfur hierarchical spheres with an ultrahigh specific surface area can controllable synthesized by changing the addition quantity of PVP. The obtained products are systematically studied by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy ( SEM), transmission electron microscopy (TEM), UV-vis absorption spectroscopy (DRS), Fluorescence (FL) and Brunauer-Emmett-Teller (BET). The photocatalytic activity of the as-prepared samples is evaluated by photocatalytic degradation of Rhodamine B (RhB) aqueous solution under visible light illumination. The results indicate that the morphology, specific surface area, photo absorbance ability, the separation efficiency of photogenerated carriers and the reactant adsorption performance can be controlled by varying the addition quantity of PVP. When 200 mg PVP is added, alpha-sulfur hierarchical spheres with uniform particle size about 1 pm and ultrahigh specific surface area of 67.1 m(2)/g is obtained, and its photocatalytic activity reaches a maximum value, which can be attributed to the combined effects of photo absorbance ability, the separation efficiency of photogenerated carriers and the reactant adsorption performance. (C) 2015 Elsevier B.V. All rights reserved.