A simple method was developed to prepare the uniform hematite hollow submicro-spheres with controllable structure and different diameter based on monodisperse poly(styrene-co-acrylic acid) [P(St-co-AA)] particles. The structure and formation mechanism of the hollow spheres were investigated in detail. The control mechanism of shell thickness was also discussed. The results indicated that the shell thickness and coarseness of the synthesized core-shell hematite hollow spheres could be tuned simply by the surface carboxyl content of the P(St-co-AA) particles. This method provided a new approach for the structure control in the preparation of hollow spheres. A Brunauer-Emmett-Teller (BET) test shows that the prepared hollow spheres have large surface areas which were decreased along with the increase of the diameter. The magnetic properties of the as-obtained hematite hollow spheres were investigated. The result showed that the coercivity and saturated magnetization were increased along with the increase of the shell thickness, and the remanent magnetization was increased along with the decrease of the diameter. A simple method was developed to prepare the uniform hematite hollow submicro-spheres with controllable structure and different diameter based on monodisperse poly (styrene-co-acrylic acid) [P (St-co-AA)] particles. The structure and formation mechanism of The control mechanism of shell thickness was also discussed. The results indicated that the shell thickness and coarseness of the synthesized core-shell hematite hollow spheres could be tuned simply by the surface carboxyl content of the P (St This method provides a new approach for the structure control in the preparation of hollow spheres. A Brunauer-Emmett-Teller (BET) test showed that the prepared hollow spheres have large surface areas which were decreased along with the increase of the diameter. The magnetic properties of the as-obtained hematite hollow spheres were investigated. The result showed that the coercivity and saturated magnetization were increased along w ith the increase of the shell thickness, and the remanent magnetization was increased along with the decrease of the diameter.