Abstract: Aiming at the high value-added utilization of coal fly ash (CFA), the performance and reaction mechanism of key metals in asymmetric electrochemical recovery were explored. The low-temperature activation of major metal elements in CFA was first achieved using NH₄F, and leaching treatment was carried out with an ethylenediaminetetraacetic acid (EDTA) solution. Based on this, an asymmetric electrochemical system based on modified carbon felt electrode was developed to electrochemically recover metal elements from the solution. The effects of NH₄F activation temperature, EDTA concentration, liquid-solid ratio and other factors on the extraction performance of metal elements in CFA were investigated. The X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), and Fourier Transform Infrared Spectroscopy (FTIR) results showed that the Si—O—Al network was effectively disrupted, resulting in an increase in the proportion of weakly acidic extracted states of Al, Fe, and Ti to 42.8%, 76.5%, and 95.2%, respectively; The reaction results showed that the leaching rates of Al, Fe, and Ti were 31.83%, 72.08%, and 94.40%, respectively, at an activation temperature of 80 ℃. Continuing to optimize the electrochemical recovery system showed that under the conditions of 0.2 mol/L EDTA, liquid-solid ratio of 15∶1, 80 ℃, and 260 r/min, the leaching efficiency increased by more than 30% compared to acid leaching. Combining Visual MINTEQ to elucidate the EDTA metal coordination mechanism, the results show that the asymmetric electrochemical system developed in this study can achieve a synergistic effect of "adsorption reduction regeneration" through periodic potential regulation, and enhance selectivity by utilizing the surface chemical properties of functionalized electrodes, achieving effective separation and recovery of metals. In addition, under optimized conditions, the recovery rates of Al and Fe reached 95.6% and 86.3%, respectively, and the current efficiency increased by more than 40%. After 5 cycles, the electrode can be restored to over 85% through acid washing and electrochemical repair. The research provides a new path for the mild and efficient resource utilization of CFA.