The application discloses a treatment method of Cu-EDTA heavy metal complex wastewater. The treatment method comprises the following steps: firstly, synthesizing a piezoelectric composite of barium titanate/graphene by a hydrothermal method; under pressure provided by ultrasonication, breaking down heavy metal complexation and degrading organic matter obtained after breakdown by virtue of the piezoelectric chemical effect of piezoelectric material; and further adsorbing and recovering free Cu<2+> or weak complex Cu<2+> by graphene in a solution obtained by breakdown and degradation, so as to effectively remove Cu-EDTA heavy metal complex wastewater. According to the application, by coupling the piezoelectric effect and the chemical process as well as the adsorption and electric desorptioneffects, the situation of high cost, cumbersome process, serious secondary pollution and secondary recovery of a traditional heavy metal wastewater treatment method is broken through, the effective removal of EDTA and the efficient recovery of Cu<2+> are implemented, the shortcomings of traditional technology are overcome, and as a green and efficient processing technology, the treatment method provides a new development direction for novel water treatment technology.