Zeolitic imidazole frameworks (ZIFs) create broad platforms to study electrochemical energy storage for their numerous advantages (e.g., their high surface area, hierarchical porous structures and flexibility templates). In the present study, metal-coordinated ZIF-derived Bimetal-Organic Framework exhibiting a well-defined morphology of rhombic dodecahedron was facilely synthesized through the addition of a certain molar ratio Ni2+ or Mg2+ when ZIF-67 was being grown. Via pyrolysis, the bimetallic composite materials, i.e., NiCo2O4@C and MgCo2O4@C were produced, exhibiting bimetallic active sites, large surface area and conductive carbon frameworks. When acting as the anode materials in lithium-ion batteries, the produced composite materials displayed excellent durability and greater specific capacity. The mentioned excellent electrochemical performances were contributed to by the stable carbon frameworks because of their greater electronic conductivity and higher electrochemical activity. Moreover, the present study presented novel ideas to synthesize the identical type of MOFs materials and can broaden their applications.