A new route to manufacture hematite (α-Fe2O3) hollow spheres with a diameter of approximately 165 ± 29 nm is presented. The proposal is based on the use of polystyrene spheres as a hard template and ethylene glycol as a solvent. In the intermediate stage of the synthesis, the PS@Fe(OH)3 sample was manufactured. For this sample, transmission electron microscopy and scanning electron microscopy confirmed the good uniformity of the polystyrene core coating, which has a thickness of approximately 12 ± 5 nm. EDS mapping confirmed the presence of iron and oxygen. The shell composition (α-FeOOH) was confirmed by Raman spectroscopy and FTIR. In the final stage of the synthesis, the Void@Fe2O3 sample was obtained. For this sample, core removal and the shell thickness (16 ± 5 nm) were confirmed by electron microscopy. EDS mapping confirmed the presence of iron and oxygen, in addition to indicating the complete removal of the polystyrene core. XRD and Raman measurements confirmed that the shell is constituted of hematite with traces of iron hydroxide. These results demonstrate the success of the adopted strategy for the synthesis of hematite hollow spheres.