Copper-containing industrial wastewater, characterized by strong acidity, high ionic strength, and various competing metals, presents significant challenges for Cu(II) recovery. To address these issues, an electric field-enhanced ultrafiltration process was developed, assisted with a functional polyelectrolyte with high selectivity for Cu(II). The polyelectrolyte, termed PPEI, was synthesized by grafting picolyl groups onto polyethyleneimine (PEI), enhancing its affinity for Cu(II). The captured Cu(II) was subsequently recovered through electrolysis, demonstrating a sustainable approach for both Cu recovery and PPEI recycling. The synthesis and stability of PPEI were confirmed through infrared spectroscopy, particle size analysis, and dialysis validation, ensuring its reliability in practical applications. The incorporation of picolyl groups onto PPEI enhances its selectivity for Cu(II) via coordination with two amines and four pyridyl groups per copper ion. Under acidic conditions, the maximum loading ratio of copper to PPEI is 1:4 with loading capacity of 119.4 mg/g, which increases to 1.5:4 (i.e., 179.1 mg/g) under neutral to alkaline conditions due to the deprotonation of excess amines. PPEI effectively removes Cu(II) from solutions under various harsh conditions at the loading ratio of 4, maintaining 92-98 % removal efficiency in the presence of high salt concentrations (up to 1 M NaCl) and pH as low as 1, and approximately 85 % removal in solutions with competing metal ions at concentrations up to 50 times higher than Cu(II). Scanning electron microscopy and membrane flux changes indicated that the application of a positive electric field significantly reduces membrane fouling and enhances Cu(II) selectivity. The application of a +0.2 V voltage to the membrane side reduced the flux decline rate by 58 %, significantly improving membrane performance while maintaining a Cu(II) removal efficiency of over 95 %. Electrolysis optimized at a current density of ≤0.004 A/cm