Porous hematite (alpha-Fe2O) hollow spheres and nanofibers could be obtained via electrospinning and subsequent thermal decomposition in air. The precursor could be fabricated by electrospinning using Fe(NO3)(3) as the iron source and Polyvinylpyrrolidone (PVP) as a complexing reagent. Upon calcination, pure porous alpha-Fe2O3 hollow spheres and nanofibers could be obtained at 650 degrees C for 3 h. The novel hollow spheres have an abundantly porous structure as well as large surface areas. Benefitting from the special porous structure, narrow bandgap, and higher surface area, porous alpha-Fe2O3 hollow materials are used as visible-light-responsive photocatalysts. So we have investigated the visible light photodegradation behavior of porous hematite (alpha-Fe2O3) hollow spheres and nanofibers towards organic dyes, as Rhodamine B (RhB). The synergetic effects of higher surface area, pore structures promoted the photocatalytic efficiency for RhB degradation under visible light and contributed to achieving the enhanced and stable photocatalytic activity.