Transition metal oxides have received considerable attention as promising electrode materials for the next generation high performance lithium-ion batteries and supercapacitors. However, transition metal oxides electrodes usually suffer from severe volume expansion and poor electrical conductivity, leading to fast capacity fading and low rate capability, which limit their commercialization in energy storage devices. Herein, we develop a bifunctional ZnONiO microsphere electrode with yolk-shelled structure for lithium-ion batteries and supercapacitors by annealing tetracyanide-metallic-frameworks precursor of Zn[Ni(CN)4]. Benefiting from its unique structure and composition, the yolk-shelled ZnONiO microspheres as anode for lithium-ion batteries exhibits a high lithium storage capacity (978 mAh g−1 at 0.25 C) and superior rate performance (628 mAh g−1 at 2.5 C after 300 cycles). While for supercapacitors electrode, it delivers a high specific capacitance of 1350 F g−1 at a current density of 3.0 A g−1 and an excellent cycling stability with a capacity retention of 92.8% over 6000 cycles. The excellent electrochemical performance is ascribed to the synergistic effect between ZnO and NiO, and the yolk-shelled structure, which can provide rich active sites for electrochemical reaction, and effectively alleviate the volume expansion and structural pulverization of the electrode during charge-discharge cycling.