Abstract: Metal-organic frameworks (MOFs) with a high porosity and high specific surface area are widely employed as anode materials in Li-ions batteries. Recently, many high capacity and high performance anode materials of Li-ion batteries have been reported, while the origin of the high capacity remains unclear. Herein, we synthesized bimetallic CoNi-MOFs via a general solvothermal method, and the obtained CoNi-MOFs show a lamellar bulk structure. The CoNi-MOFs exhibit a remarkable electrochemical performance, with a high reversible capacity up to 1 120 mA·h/g after 200 cycles performed at a current density of 500 mA/g and an excellent rate performance. The valence states of Ni and Co change between +2 and 0 during the charging and discharging process, which implies the frameworks completely collapse, and it is further determined by the XRD detection. It is clearly discovered that the huge amount of amorphous Li metal was assembled in the anode materials through the time-of-flight secondary ion mass spectrometry (TOF-SIMS), which further provides the large capacity and high rate performance. X-ray absorption spectroscopy (XAS) experiments were conducted using the Beijing Synchrotron Radiation Facility (BSRF) to investigate the valence state changes and structural evolution processes of Co and Ni. These techniques significantly enhance the understanding of battery material reaction mechanisms and enhance the design and optimization of battery materials.