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A three-dimensional (3D) porous structure that designed based on MnCo 2 O 4 decorated graphene was synthesized by a two-step method. The precursor was prepared of MnCo 2 O 4 by solid phase synthesis method, then in the hydrothermal reaction course, the graphene nanosheets as well as this precursor were self-assembled into a 3D interconnected network. The resultant composite materials present a higher specific capacitance (503 F g−1 at 1 A g−1 current density) and an excellent cycling stability. After 5000 charge/discharge cycles at a current density of 10 A g−1, 97.4% of the specific capacitance was retained. Thus, this material has a promising application potential for supercapacitor, at the same time, this synthetic method can also provide an idea for synthesizing composites based on 3D graphene in the future. • Three-dimensional composites of MnCo 2 O 4 and graphene were synthesized. • Three-dimensional graphene provides a porous skeleton. • The MnCo 2 O 4 /3DG electrode exhibits excellent electrochemical properties. • The excellent supercapacitor performance is attributed to the synergistic effect. [ABSTRACT FROM AUTHOR]