The present study manifests an innovative and green approach to graft metal ion adsorbent, polyethylenimine (PEI), onto an electrospun chitosan (CS)/polycaprolactone (PCL) composite membrane via atmospheric pressure nitrogen plasma grafting polymerization. FTIR absorption peak at around 1690 cm−1 was attributed to the bending vibration of N-H from PEI. Since the plasma exposure time is a dependent factor of –NH bond formation, an increased nitrogen content up to 3.3% was observed with an extensive reaction time under plasma treatment. In addition, N1s spectra showed a clear PEI dominating characteristic at 401.7 eV, which suggested a successful grafting of PEI onto the CS/PCL membrane. According to the EDX analysis, a significant amount of copper ions was detected in PEI-CS/PCL membranes. This study showed that a greener wastewater treatment can be realized with the developed plasma synthesis technology.