The alternating adsorption of oppositely charged molecular species, known as the electrostatic layer-by-layer (LBL) process, is a simple and elegant method of constructing highly tailored ultrathin polymer and organic-inorganic composite thin films. We use this method to manipulate transport and function in thin films, enabling the generation of a range of organic and organic-inorganic devices. Several approaches to the controlled manipulation, construction and, in some cases, the controlled deconstruction, degradation or dissolution of multilayers upon specific stimulus will be discussed. A modified form of the automated alternate misting approach is also useful for the incorporation of materials systems and the generation of complex thin film morphologies and architectures. New developments in the rapid assembly of these systems with nanoscale objects such as carbon nanotubes and functionalized nanoparticles, and their practical applications from biomedical implants and modular release systems to electrochemical energy devices will be addressed.