The traditional hydrometallurgical process is the mainstream technology to recover precious metals from e-waste, which usually adopts strong acid/base and strong oxide with high environmental cost and energy consumption. In the present study, the selective extraction of precious metals was simulated and experimented with DMF as the solvent and Cl⁻ ions provided by CaCl₂ and CuCl₂ (oxidizing agent). The leaching and precipitation rates of precious metals (Au, Ag, Pd) can reach more than 98% under optimization conditions. Kinetic data shows that the control model of the leaching process on precious metals was determined by linear fitting of the shrinkage model. The complex trace precious metals were extracted selectively using dimethylglyoxime and deionized water as precipitators by the leaching-precipitation-cycle method. Meanwhile, the waste liquid produced by this reaction process could be cyclically utilized. Furthermore, the leaching mechanism of precious metals was proposed. DMF could be complexed with the metals as well as coordination ions (Cl⁻), which can reduce the redox potentials. Cu(II) could be easily reduced to Cu(I) in the DMF system due to the higher second ionization energy of copper, which is not influenced by the hydration effect, thus shifting the equilibrium to the metal leach side. Oppositely, the addition of water promoted the conversion of Cu(I) to Cu(II) since the higher hydration energy of Cu(II) compensates for the second ionization energy. This research opens up a new path of sustainable development and provides basic theory and practical experience for environmentally friendly recovery of precious metals from e-waste.