An electrolytic cell having a cation-selective membrane Neosepta CM-1 was applied to treat solutions containing equimolar amounts of CuSO4 and citric acid. The iridium oxide and platinum coated on titanium were used as the anode and cathode, respectively. The catholyte contained the citrate-chelated Cu(II) and the anolyte consisted of NaNO3. All experiments were carried out at different current densities (18.5–139 A m−2), initial catholyte pH (1.0–9.0) and Cu(II) concentration (5–30 mM), and initial anolyte NaNO3 concentration (1–200 mM). An economically acceptable current efficiency (>50%) and recovery of Cu(II) and citrate (>96%) could be obtained when the feed concentration the chelated Cu(II) was sufficiently high.