The stability of surface-tethered polyelectrolyte brushes has been investigated during the past few years. We have previously reported on the degrafting of poly(acrylic acid) (PAA) polymer brushes from flat silicon substrates. Here, we present a detailed study on the effects of NaCl concentration and the grafting density and molecular weight on the stability of PAA brushes during incubation in 0.1 M ethanolamine buffer (pH 9.0) solutions. Without NaCl in the buffer solution, the PAA brushes remain intact. Adding NaCl facilitates etching of the substrate due to accelerating dissolution of the top silica layer and promoting degrafting of the PAA chains. The PAA grafting density and molecular weight play an important role in the substrate etching by affecting the penetration barrier and local concentration of the etchants. We also tested the stability of self-assembled monolayers (SAMs) made of hydrophobic alkyltrichlorosilanes anchored on silicon substrates. The results demonstrated that the SAMs were too thin to protect the substrates from etching, in contrast to thick poly(methyl methacrylate) brushes. Our findings suggest that both polymer brushes (especially polyelectrolyte brushes) and SAMs anchored to silicon substrates may undergo erosion/etching on the substrates in basic environments, which compromises their stability and therefore jeopardizes their applications in coating, biosensing, and so forth.