New developments in the area of hydrogen-bonded layer-by-layer assembly composed of weak polyelectrolytes are reviewed, with emphasis on self-assembly in an aqueous environment. Advances in fundamental understanding of polymer layering at surfaces are addressed. The effects of molecular weight of polymers, ionic strength, pH, and temperature on growth and post-self-assembly response of hydrogen-bonded films are summarized and contrasted with trends known for electrostatically assembled films. Deposition of hydrogen-bonded films onto particulate substrates and properties of produced capsules are discussed. Strategies to stabilize hydrogen-bonded multilayers at neutral and basic pH through crosslinking and response properties of produced ultrathin hydrogel films deposited onto flat substrates or comprising the wall of capsules are also described. The potential of hydrogen-bonding self-assembly in surface modification and functionalization, in construction of responsive functional containers and membranes, or as solid-state matrices demonstrating superior ion conductivity make these materials promising for future biomedical and device applications.