Organic polymers are widely used as coatings and adhesives to metal surfaces, but aluminum is among the most difficult substrates because of rapid oxidative passivation of its surface. Poly(1,4-disubstituted 1,2,3-triazoles) made by copper-catalyzed azide–alkyne cycloaddition form strongly bonded interfaces with several metal substrates. In this work, a variety of alkyne and azide monomers were explored as precursors to anticorrosion coatings for a standard high-strength aluminum–copper alloy. Monomers of comparatively low valency (diazide and trialkyne) were found to act as superior barriers for electrolyte transfer to the aluminum surface. These materials showed excellent resistance to corrosive pitting due to the combination of three complementary properties: good formation of highly cross-linked films, as observed by Fourier transform infrared spectroscopy and differential scanning calorimetry; good adhesion to the aluminum alloy substrate, as shown by pull-off testing; and excellent impermeability, as demonstrated by electrochemical impedance spectroscopy.