A polyethyleneimine/poly(acrylic acid) (bPEI/PAA) multilayer coating was assembled on copper by layer-by-layer assembly and its anticorrosion performance and self-healing behavior investigated in 500 mM NaCl solution using multiple techniques including scanning electron microscopy, electrochemical impedance spectroscopy, equivalent circuit modeling, potentiodynamic polarization measurements, and cyclic voltammetry. In 500 mM NaCl solution, the coating could not only effectively prevent corrosion of copper by increasing the charge-transfer resistance and inhibition effectiveness of the system, but also spontaneously repair damage with a width of about 50 μm within 1 h. It is hoped that these findings will indicate a route for preparation of novel anticorrosion coatings with self-healing ability.