The printed circuit boards (PCBs) contains large number of heavy metal such as Cd, Cr, As, Ni, Zn and Mn. In this study, the use of electrokinetic (EK) treatment with different assisting agents has been investigated to recover the heavy metals from waste PCBs, and the effectiveness of different assisting agents (HNO(3), HCl, citric acid) was evaluated. The PCBs were first pre-treated by supercritical water oxidation (SCWO) process, then subjected to EK process. The heavy metal speciation, migration and recovery efficiency in the presence of different assisting agents during EK process were discussed. The mass loss of Cd, Cr, As and Zn during the SCWO process was negligible, but approximately 52% of Ni and 56% of Mn were lost in such a process. Experimental results showed that different assisting agents have significant effect on the behavior and recovery efficiency of different heavy metals. HCl was highly efficient for the recovery of Cd in waste PCBs due to the low pH and the stable complexation of Cl(-). Citric acid was highly efficient for the recovery of Cr, Zn and Mn. HNO(3) was low efficient for recovery of most heavy metals except for Ni.