Separation of metal from industrial sludges by hydrometallurgical process is usually complicated by the presence of polymeric coagulant added during wastewater treatment. In this study, a process was proposed for the recovery of copper from the sludge of the printed wiring board industry. The sludge was first leached with citric acid solution to extract copper and zinc. The leachate was further purified using a D(2)EHPA-modified Amberlite XAD-4 resin. During the leaching process, more than 87% and 79% of Cu and Zn, respectively, were dissolved by citric acid solution. Dissolution kinetics showed that the extractions of Cu and Zn could be described by second-order extraction. The low activation energies indicate that the dissolutions of Cu and Zn may be diffusion controlled. The ion-exchange isotherm showed that D(2)EHPA-modified Amberlite XAD-4 resin has a higher Zn ion selectivity tha n Cu. The selective separation results demonstrated that D(2)EHPAmodified Amberlite XAD-4 resin could preferentially remove Zn in the practical leachate, leaving only Cu ion in the solution.