The present study reports a mechanochemical (MC) process for effective recovery of copper (Cu) and precious metals (i.e. Pd and Ag) from e-waste scraps. Results indicated that the mixture of K2S2O8 and NaCl (abbreviated as K2S2O8/NaCl hereafter) was the most effective co-milling reagents in terms of high recovery rate. After co-milling with K2S2O8/NaCl, soluble metallic compounds were produced and consequently benefit the subsequent leaching process. 99.9% of Cu and 95.5% of Pd in the e-waste particles could be recovered in 0.5mol/L diluted HCl in 15min. Ag was concentrated in the leaching residue as AgCl and then recovered in 1mol/L NH3 solution. XRD and XPS analysis indicated that elemental metals in the raw materials were transformed into their corresponding oxidation state during ball milling process at low temperature, implying that solid–solid phase reactions is the reaction mechanism. Based on the results and thermodynamic parameters of the probable reactions, possible reaction pathways during ball milling were proposed. Suggestion on category of e-waste for ball milling process was put forward according to the experiment results. The designed metal recovery process of this study has the advantages of highly recovery rate and quick leaching speed. Thus, this study offers a promising and environmentally friendly method for recovering valuable metals from e-waste.