The Co oxide microfibers were synthesized using the electrospinning process and formed $Co_3O_4$ microfibers after being calcined at high temperatures. The calcination temperature influenced the diameters, morphology, crystalline phase, and chemical environment of the fibers. The surface morphology of the obtained fibers was examined by using the scanning electron microscope (SEM). As the calcination temperatures increased from room temperature to 873 and 1173 K, the diameters of the cobalt oxide fibers decreased from 1.79 to 0.82 and 0.32 mm, respectively. The structure of the fibers was investigated with X-ray diffraction (XRD) and transmission electron microscopy (TEM). The calcined $Co_3O_4$ fibers had crystalline face-centered cubic (fcc) structure. The X-ray photoelectron spectroscopy (XPS) results revealed that increasing the calcination temperature promoted the formation of $Co^{2+}$ and $Co^{3+}$ species.