Porous hollow Co₃O₄ with rhombic dodecahedral structures were prepared by the calcination of ZIF-67 ([Co(mim)2; mim = 2-methylimidazolate]) rhombic dodecahedral microcrystals. A supercapacitor was successfully constructed by adopting the resulting porous hollow Co₃O₄ rhombic dodecahedral structure as the electrode material, which showed a large specific capacitance of 1100 F g(-1) and retained more than 95.1% of the specific capacitance after 6000 continuous charge-discharge cycles. The excellent capacitive properties and stability mark the porous hollow Co₃O₄ with the rhombic dodecahedral structure as one of the most promising electrode materials for high-performance supercapacitors.