Polymer-clay nanocomposites, described as the inclusion of nanometer-sized layered silicates into polymeric materials, have been widely researched due to significant enhancements in material properties with the incorporation of small levels of filler (1 - 5 wt.%) compared to conventional micro- and macro-composites (20 - 30 wt.%). One of the most promising applications for polymer-clay nanocomposites is in the field of barrier coatings. The development of UV-curable polymer-clay nanocomposite barrier coatings was explored by employing a novel in situ preparation technique. Unsaturated polyesters were synthesized in the presence of organomodified clays by in situ intercalative polymerization to create highly dispersed clays in a precursor resin. The resulting clay-containing polyesters were crosslinked via UV-irradiation using donor-acceptor chemistry to create polymer-clay nanocomposites which exhibited significantly enhanced barrier properties compared to alternative clay dispersion techniques. The impact of the quaternary alkylammonium organic modifiers, used to increase compatibility between the inorganic clay and organic polymer, was studied to explore influence of the organic modifier structure on the nanocomposite material properties. By incorporating just the organic modifiers, no layered silicates, into the polyester resins, reductions in film mechanical and thermal properties were observed, a strong indicator of film plasticization. An alternative in situ preparation method was explored to further increase the dispersion of organomodified clay within the precursor polyester resins. In stark contrast to traditional in situ polymerization methods, a novel "reverse" in situ preparation method was developed, where unmodified montmorillonite clay was added during polyesterification to a reaction mixture containing the alkylammonium organic modifier. The resulting nanocomposite films exhibited reduced water vapor permeability and increased mechanical properties. The novel preparation of hybrid films coupling the advantageous properties of organic-inorganic hybrids formed through sol-gel chemistry with polymer-clay nanocomposite technology was also explored. Alkoxysilane-functional copolymer-clay nanocomposites were first synthesized, followed by crosslinking via simultaneous hydrolysis and condensation reactions to create the novel hybrid barrier films. By dispersing organomodified clay throughout the hybrid network, dramatic improvements in several film properties were observed, particularly regarding the viscoelastic properties. Additional studies with the same organic-inorganic preparation technique were performed to incorporate amine-functionality into the hybrid film for potential applications as protective membranes in carbon dioxide capture and separation technologies. Finally, controlled free-radical polymerization techniques were combined with the preparation of the organic-inorganic hybrids.