A new route to manufacture α-Fe2O3 hollow spheres with 142 nm in diameter was presented. The proposal is based on the methodology described by Yoshikawa in combination with the paper published by Kobayashi and using polystyrene spheres (PS with 200 nm in diameter) as a hard template. The transmission electron microscopy, Raman spectroscopy and UV-Vis analyses, indicated the intermediate stage with product formed by a spherical 12 nm shell (α-FeOOH) supported on the PS surface (YK200a sample). At the final stage, the α-Fe2O3 hollow spheres without PS template showed some traces of alpha iron hydroxide (YK200b sample). The detection of crystalline phase was possible by using X-ray diffraction combined and Raman spectroscopy.