Perforated polygonal cobalt oxide (Co3O4) is synthesized using electrospinning and a hydrothermal methodfollowed by the removal of a carbon nanofiber (CNF) template. To investigate their formation mechanism, thermogravi-metric analysis, field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy are examined. To obtain the optimum condition of perforated polygonal Co3O4, we pre-pare three different weight ratios of the Co precursor and the CNF template: sample A (Co precursor:CNF template-10:1), sample B (Co precursor:CNF template-3.2:1), and sample C (Co precursor:CNF template-2:1). Among them, sam-ple A exhibits the perforated polygonal Co3O4 with a thin carbon layer (5.7-6.2 nm) owing to the removal of CNF tem-plate. However, sample B and sample C synthesized perforated round Co3O4 and destroyed Co3O4 powders, respectively,due to a decreased amount of Co precursor. The increased amount of the CNF template prevents the formation of polygonalCo3O4. For sample A, the optimized weight ratio of the Co precursor and CNF template may be related to the suc-cessful formation of perforated polygonal Co3O4. Thus, perforated polygonal Co3O4 can be applied to electrode materialsof energy storage devices such as lithium ion batteries, supercapacitors, and fuel cells.