The excellent electrical conductivity of graphene is due to its highly-conjugated structures. Manipulation of the electronic and mechanical properties of graphene can be achieved by controlling the destruction of its in-sheet conjugation system. Herein, we report the preparation of CoCeS x À SA@BPMW@RGO through π-π stacking interactions at the molecular level. In this study, sodium alginate was reacted with Co 2 + and Ce 3 + , and the composite was loaded onto a graphene surface. The graphene sheets were prepared using a bi-pyrene terminated molecular wire (BPMW) to avoid re-stacking of the grapheme sheets, thereby forming nanoscale spaces between sheets. The angle between the BPMW coplanar pyrene group and the phenyl group was 33.2°, and the graphene layer is supported in an oblique direction. Finally, a three-dimensional porous composite was obtained after annealing and vulcanization. The obtained CoCeS x À SA@BPMW@RGO exhibited excellent electrical conductivity and remarkable cycle stability. When the current density was 1 A g À 1 , its specific capacitance was as high as 1004 F g À 1 . BPMW modifies graphene through the synergistic effect of π-π stacking interaction and special structure to obtain excellent electrochemical performance. Moreover, a solid-state asymmetric supercapacitor device was fabricated based on the synthesized CoCeS x À SA@BPMW@RGO hybrid, which exhibited a power density of 979 W kg À 1 at an energy density of 23.96 Wh kg À 1 .