Developing bifunctional electrocatalysts of high-efficiency and new structures for overall water splitting are highly desirable and ongoing challenge. Herein, CoxNi10-x, layer double hydroxide salts with controllable structure and morphology induced by 2-methylimidazole to derive ZIF-67 on Ni/Fe foam is reported. The asprepared 3D CoxNi10-x, layer double hydroxide microspheres are constructed by self-assembly of 2D nanoflake and 1D nanorod with ZIF-67 particles due to the double influence of Ni and 2-methylimidazole. It is discovered that the Ni and 2-methylimidazole can simultaneously modulate morphology and structure of CoxNi10-x layer double hydroxide to distinctly increase the electrochemical active surface area for exposing more accessible active sites. Notably, the 3D microsphere heterogeneous catalysis of the self-assembly combines the merits of low dimensions (1D and 2D) materials, providing high structural void porosity and fast charge transport channels. Particularly, the Co7Ni3 layer double hydroxide salts@ZIF-67/Ni/Fe foam exhibits the highest electrocatalytic activity with the lower overpotentials of 260 and 165 mV toward oxygen evolution reaction and hydrogen evolution reaction at current density of 10 mA cm(-2), respectively. The outstanding activity originates from the strong electronic coupling between the 3D microsphere and ZIF-67. This work can bring a new prospect for fabricating highly-active and new structure electrocatalysts.