Nano-thin coatings of glutaraldehyde (GA)-crosslinked polyethyleneimine (PEI) are extremely selective and effective in binding copper from seawater. Here it was demonstrated that GA-PEI performs significantly different from PEI. The copper-selectivity of self-assembled PEI coatings on silicon substrates was greatly improved by GA-crosslinking. After submersion in artificial seawater containing 200 ppb copper and equimolar amounts of 11 competing ions only copper and trace amounts of Zn were detected in the GA-crosslinked coatings, while for non-crosslinked PEI there was about 30% Zn present relative to copper. The coatings were demonstrated to be highly stable under acidic conditions and retained their copper-binding selectivity after repeated cycles of binding and acid-mediated elution. After self-assembly of the GA-crosslinked coating on mesoporous diatomaceous earth particles, significant amounts of copper could be extracted from 200 ppb in artificial seawater and eluted under acidic pH. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43954. © 2016 Wiley Periodicals, Inc