In this contribution, hierarchical CoFe 2 O 4 particles are successfully prepared via modified polyol elaboration methods with NaBH 4 and proposed heat treatment process. Here, new asprepared CoFe 2 O 4 particles with a size range of 5µm show high uniform characterization of size, shape and cubic spinel crystal structure by X-ray diffraction (XRD), whole pattern fitting and Rietveld refinement, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). We discover that CoFe 2 O 4 microparticles prepared in the certain size range of 5µm show exciting configurations of grain and grain boundary under particle heat treatment at high temperature 900°C. Finally, CoFe 2 O 4 ferrite particles with various well-defined micro and nanoscale structures were produced at appropriate heat treatment processes under high temperature, which has high coercive field, H C around 416-888 Oe, and the highest saturation magnetization, M S about 74-91 emu g -1 at room temperature (RT) for all the as-prepared samples by vibrating sample magnetometer (VSM). Here, the magnetic behavior has shown persuasive evidences that desirable ferrimagnetic properties of CoFe 2 O 4 oxides do not only depend on their size but also the spinel structure of CoFe 2 O 4 oxides as well. Finally, the as-prepared CoFe 2 O 4 particles with the formula CoO.Fe 2 O 3 were regarded as the best inverse ferrimagnetic materials with magnetic parameters of H C at 896 Oe, M R /M S squareness around 0.420, M S around 92 emu g -1 at 20 kOe for the downward part of hysteresis loop.