Shape tailoring of active materials could alter the performance of supercapacitors. Herein, we report the ethylenediaminetetraacetic acid (EDTA) assisted hydrothermal approach for the synthesis of single crystalline CuCo2O4 octahedrons and their application in a supercapacitor. Morphology and BET surface area analysis demonstrates the formation of CuCo2O4 octahedrons with a surface area of 61.97 m2 g−1. As an active material, the CuCo2O4 octahedrons exhibited a high specific capacity of 989 C g-1 at 5 mV s−1. In addition, a long-term cyclic stability with 87% of its initial specific capacity retention was achieved after 5000 cycles at 10 A g−1. This outstanding performance could be ascribed to its unique octahedron morphology. The electrochemical results demonstrate that CuCo2O4 with such a unique octahedron architecture could be a potential active material for the development of a high performance supercapacitor.