Methods for the layer-by-layer deposition of oppositely charged polymers on surfaces can be used to assemble thin multilayered films using a broad range of natural, synthetic, and biologically relevant materials. These methods also permit precise, nanometer-scale control over the compositions and internal structures of multicomponent assemblies. Provided that the individual components of these materials are selected or designed appropriately, these methods provide tantalizing new opportunities to design thin films and coatings that provide spatial, temporal, or active control over the release of one or several different agents from surfaces. The last two years have seen a significant increase in reports describing the development of new chemical, physical, and biomolecular approaches to the controlled erosion, triggered disassembly, or general deconstruction of multilayered polymer films. In this Progress Report, we highlight recent work from our laboratory and several other groups toward the design of ultrathin multilayered assemblies that i) permit broad, tunable, and sophisticated control over film erosion, and ii) provide new opportunities for the localized release of macromolecular therapeutics, such as DNA and proteins, from surfaces.