As FeOx particles were prepared by oxidation-reduction reaction, the surfactant of polyethylene glycol (ab. PEG) was used to cover the FeOx particles, thus the PEG/FeOx ferrofluids were obtained. The morphology, structure and composition of the ferrofluids were investigated. The results show that the product is spheric in the shape, and the diameter of the product is obviously influenced by PEG content and slightly influenced by the stirring rate. When the content of PEG increases in the range of 50～350g/L, the diameter of the product decreases. However, when the content of PEG is in the range of 350～750g/L, the diameter increases with the increasing of PEG content. When the stirring rate is between 50 and 150r/min, the diameter of the product slightly decreases as the stirring rate increases. Moreover, the results demonstrate that the products are mainly constituted of PEG and FeOx, and the value of x in the formula of FeOx can be adjusted by controlling the molar ratio of H2O2 to Fe2+. Further analysis indicates that the organic and inorganic components of the PEG/FeOx ferrofluids are combined by both physical adsorption and coordinate combination.