<p>To respond to the issue of weak conductivity and structural instability of MOF materials applied in the intrinsic characterization of lithium-ion batteries. In this paper, Ni-MOF and its complex with graphene (Ni-MOF/GR) have been successfully synthesized by one-step solvothermal method, which improved the electrochemical performance of Ni-MOF electrode. The morphology, structure, and composition of the electrode were also determined using SEM, XRD, FTIR, and XPS. Binding energy of Ni-MOF/GR is calculated to reach − 0.79&#xa0;eV by density-functional theory (DFT). Graphene (GR) transfers charge 1.017 e to Ni-MOF. Simultaneous characterization by the four-probe method revealed that GR addition increased the conductivity by eight orders of magnitude (4.81 × 10⁻⁸–6.00 S/cm), which is consistent with the density of states (DOS) calculations. In comparison with the intrinsic Ni-MOF, cycling and rate properties of Ni-MOF/GR composite anode were substantially enhanced. When the charge/discharge test was conducted at 5 C rate, Ni-MOF/GR retained a discharge specific capacity up to 368.4 mAh g⁻¹ despite 500 cycles, nearly two times more than Ni-MOF (only 185.1 mAh g⁻¹). Additionally, the average specific capacity of Ni-MOF/GR material (958.01–500.66 mAh g⁻¹) showed a higher recovery rate than that of pristine Ni-MOF (1106.7–297.38 mAh g⁻¹) when charge/discharge tests were performed at different rates. In this work, it is shown that composite GR can improve the electronic conductivity and structural stability of materials, which is indispensable for enhancing the capacity, rate performance, and cycling stability of materials.</p>