Electroplating wastewater often contains such complex agents as EDTA and some heavy metals exist in complexing form, which present great challenge for heavy metal removal. Given the low cost and satisfying effect of microelectrolytic method in processing complex wastewater, iron-copper microelectrolysis was adopted to treat the EDTA complex copper solution. Analysis of the change of metal ions and the infrared spectrum of the precipitates during microelectrolysis showed that the major changes occurred were iron dissolution, increased concentration of Fe²⁺ and Fe³⁺, decreased Cu²⁺ concentration, accompanied by a slight decrease in EDTA concentration and the formation of Fe(OH)₃ precipitate. MINTEQ software was used to simulate the complex morphological distribution. The results show that the addition of Fe³⁺ can make Cu²⁺ into a free state. The larger the Fe³⁺/Cu²⁺ is, the lower the pH is, hence the better the removal effect. The addition of Fe²⁺ under alkaline conditions can make Cu²⁺ become Cu(OH)₂. The greater the Fe²⁺/Cu²⁺ is, the higher the pH is, the better the removal effect. Combining with the experimental and simulation results, it can be concluded that the desorption of Fe³⁺ under acidic conditions and the reduction of free Cu²⁺ by iron scrap are the main reasons for the removal of Cu²⁺-EDTA by microelectrolysis.