Using a layer-by-layer sequential adsorption technique, we report the construction of hybrid films in which layers of hydrogen-bonded polymers are embedded within electrostatically associated polyelectrolytes. The components of the hybrid film include a neutral hydrogen-bonding polymer, a weak polycarboxylic acid, and a strong polycation. Depending on the pH value used for the deposition of the electrostatic film, we found two distinctive regimes of film growth. At pHs lower than a critical value, deposition of electrostatic layers occurred on top of hydrogen-bonded stacks to produce hybrid, three-component films. At pHs higher than a critical value, neutral, hydrogen-bonded chains were displaced by the adsorbing chains of the polycation, producing two-component films. The property of the hydrogen-bonded stacks of hybrid films to be selectively dissolved by exposing them to a high pH makes these films promising candidates for producing free polyelectrolyte films.