A series of Co-Sn substituted barium ferrite particles have been successfully synthesized by a reverse microemulsion technique. The effects of heteroatom contents and precipitating agents were investigated, respectively. It was found that the presence of heteroatoms could enhance lattice parameters, affect morphology evolution and modulate magnetic properties. Particularly, an unusual saturation magnetization (>70.0 emu/g) could be achieved undertow heteroatoms concentration due to preferential occupation in specific sites. Precipitating agents played a critical role in forming barium ferrite phase, only sufficient precipitating agents could produce high-purity phase. Besides, this method is not limited in the synthesis of Co-Sn substituted barium ferrite, it can be extended to other heteroatoms, such as Ni-Zr and La, and resultant products also show well crystalline phase and unique magnetic properties. (C) 2011 Elsevier Ltd. All rights reserved.