Binary transition metal oxides as electroactive materials have continuously aroused grumous attention due to their high theoretical specific capacitance, high valtage window, and multiple oxidation states. However, the tiny specific surface area, poor conductivity and unsatisfactory cycle stability limit their practical application. Hence, a synthetic strategy is designed to fabricate a dual-tasking hollow cube nickel ferrite (NiFe2O4) - based composite (NiFe2O4-NiCo-LDH@rGO) with hierarchical structure. The composite is constructed by firstly preparing hollow NiFe2O4 from cube-like Ni - Fe bimetallic organic framework (NiFe-MOF), and then integrating nickel cobalt layered double hydroxide (NiCo-LDH) nanowires, together with reduced graphene oxide (rGO) via pyrolysis in conjuction with hydrothermal method. The NiFe2O4 possessing cubic hollow structure contributes to a huge accessible surface area, meanwhile alleviates large volume expansion/contraction effect, which facilitates suffcient permeation of the electrolyte and rapid ion/charge transport, and results in high cycling stability. The introduction of layered NiCo-LDH results in hierarchical structure and thus offers maximum contact areas with electrolyte, which heightens the specific capacitance of obtained composite and enhances the electro-catlytic activity towards oxidation of glucose. Furthermore, rGO layer greatly improves the electrical conductivity and ion diffusion/transport capability of composite. Benefiting from the unique structure and individual components of NiFe2O4-NiCo-LDH@rGO composite, the electrode delivers a high specific capacitance (750 C g-1) and superb durability. Simultaneously, the asymmetrical device based on NiFe2O4-NiCo-LDH@rGO as positive electrode delivers remarkable energy density (50 Wh kg-1). Moreover, NiFe2O4-NiCo-LDH@rGO exhibits good sensing performance with a sensitivity of 111.86 µA/µM cm-2, the wide linear range of 3.500 × 10-5 - 4.525 × 10-3 M, and the detection limit of 12.94 × 10-6 M with a signal to noise ratio of 3. Consequently, the NiFe2O4-NiCo-LDH@rGO could provide a prospective notion constructing bifunctional materials with hollow-cube hierarchical structure in the field of supercapacitors and electrochemical sensors.