Here, we propose a multi-dimensionally hierarchical self-supported Cu@Cu2+1O@Co3O4 heterostructure as superior bifunctional material for lithium-ion storage and electrocatalytic oxygen evolution via rapid in-situ oxidation-electrodeposition-annealing treatment. The 3/1/2-dimensional hybridization heterostructure rationally organized by three-dimensional Cu foam, one-dimensional Cu2+1O nanowires and two-dimensional Co3O4 nanosheets achieves remarkable synergistic interactions. In brief, the free-standing Cu foam framework enables remarkable structure robustness, electronic conductivity and electrolyte infiltration. Meanwhile, the in-situ grown Cu2+1O nanowires with excess metal defects indeed provide certain activity, effectively adjust the size and distribution of anchored Co3O4 nanosheets and dramatically shorten the diffusion pathway of ions and electrons. Moreover, the constructed interfaces between Cu2+1O and Co3O4 further yield sufficient electrochemically active surface area. In consequence, Cu@Cu2+1O@Co3O4 heterostructure delivers superior lithium-ion storage capacity and electrocatalytic oxygen evolution activity. Specifically, a prominent and stable discharge capacity of 1090 mAh g−1 can be delivered after 200 cycles at 500 mA g−1. Even when the current density is elevated to 5000 mA g−1, remarkable discharge capacity of 601 mAh g−1 still can be yielded. As for the electrocatalytic oxygen evolution activity, Cu@Cu2+1O@Co3O4 heterostructure demonstrates a particularly low overpotential of 223 mV at 10 mA cm−2 and Tafel slope of 46.3 mV dec−1. This strategy may enlighten the researchers on the further development of electrochemically active materials for advanced electrode and catalyst.