Metal-organic framework-based supercapacitors have been widely recognized as the best energy storage devices for future portable electronic equipment. Herein, CoP-T (T = 300, 350, and 400 degrees C) microcubes with a solid and hollow microstructure were successfully synthesized by low-temperature phosphorization of [CH3NH3][Co-(HCOO)(3)] precursor at desired temperatures. The morphology, structure, and composition of the prepared CoP-350 degrees C samples were analyzed by scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Hollow CoP-350 degrees C microcube has a larger specific surface area (25.9 m(2) g(-1)) than that of solid ones (16.1 m(2) g(-1)). When the two samples were used as electrode raw materials for supercapacitors, the hollow CoP-350 degrees C electrode exhibits better electrochemical performance (560 F g(-1)) than that of the solid one (427.6 F g(-1)) at a current density of 1 A g(-1). The enhanced supercapacitor properties may be attributed to the large surface area and the unique hollow structure. Further, an asymmetric supercapacitor was prepared by employing the hollow CoP-350 degrees C microcubes as anode and N-doped graphene as cathode. It has a high rate capability (capacitance retention of 69% from 0.5 to 8 A g(-1)), a high energy density (21.4 W h kg(-1) at a power density of 373 W kg(-1)), and outstanding cycling stability (remained 81.2% after 6000 cycles).