Layer-by-layer (LbL) films were prepared by an alternate deposition of phenylboronic acid-bearing poly(allylamine hydrochloride) (PBA-PAH) and poly(vinyl alcohol) (PVA) on the surface of a quartz slide to develop thin films that can be decomposed in response to hydrogen peroxide (H2O2). The PBA-PAH/PVA films decomposed in the presence of H2O2; the degree and kinetics of decomposition depend on the concentration of H2O2 and on the pH of the solution. For example, the film decomposition completely occurred in 30 min in 1.0 mM H2O2 solution at pH 7.4, while it took 180 min in 0.1 mM H2O2 solution. The H2O2-induced decomposition of the film can be explained in terms of the oxidative scission of the carbon-boron bond in PBA residues in the PBA-PAH chains. A potential use of the PBA-PAH/PVA films in developing H2O2-sensitive delivery systems was suggested.