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A novel core–shell structured Co 11 (HPO 3 ) 8 (OH) 6 –Co 3 O 4 hybrid material was synthesized in a hydrothermal condition from the microporous Co 11 (HPO 3 ) 8 (OH) 6 microrod precursor. Due to the unique nano/microstructures, the assembled asymmetric all-solid-state supercapacitor (Co 11 (HPO 3 ) 8 (OH) 6 –Co 3 O 4 and graphene) showed a high gravimetric specific capacitance of 1.84 F cm −3 at 0.5 mA cm −2 and an excellent cycling stability with only 1.3% ca decay after 3000 cycling. The device delivered a maximum power density of 105 mW cm −3 at a current density of 1.5 mA cm −2 and possessed a maximum volumetric energy density of 0.48 mW h cm −3 at a current density of 0.5 mA cm −2 . The device also exhibited excellent flexibility. [ABSTRACT FROM AUTHOR]