Abstract: Spinel ferrite ZnFe₂O₄ powders were synthesized directly from ZnO and α-Fe₂O₃ mixtures by high-energy mechanical milling(HEMM). BaZn₂Fe₁₆O₂₇(Zn₂-W) ferrite powders were prepared by HEMM and subsequent heat treatment using the mixture of BaO,Zno and α-Fe₂O₃. X-ray diffraction (XRD) was used to investigate phase structure of powder obtained from the chemical reaction processing at different milling time. It has been found that the solid reactions between metal oxides take place step by step. Grain sizes of ZnFe₂O₄ are less than 10nm. Ultrafine BaZn₂Fe₁₆O₂₇(Zn₂-W) ferrite powder (100nm~200nm) has been synthesized by HEMM and subsequent heat beatment.