Electrodeionization(EDI) is an electro-membrane process with high efficiency for deep desalinating, where water dissociation mechanism occurring on the surface of ion exchange membranes and resins typically exsits and acts. But when used to treat heavy metal-containing solutions such as effluents from the electronic industry, the EDI will suffer from metal-hydroxides precipitation which would destroy the separation process irreversible. With the primary aim to solve that problem, an electrodeionization process coupled with bipolar membrane (BMEDI) was developed together with a preacidification method. The effects of separating and concentrating heavy metal ions by the BMEDI were studied with NiSO4 solution containing 24 mg×L-1 Ni2+ ions. The results suggested that, the nickel-concentration in the dilute products were both below the analysis limit at constant current densities of 40 mA·cm-2 and 10 mA·cm-2, while a concentration factor of 31 was achieved at 40 mA·cm-2. In addition, no Ni(OH)2 precipitation was found in all the compartments throughout the experiments, which provide a guarantee of good stability for long-time operation.