The present invention is directed to methods for providing a polyelectrolyte multilayer film at a liquid-liquid interface. Such methods include steps of sequentially-depositing layers of cationic and anionic polyelectrolytes at a liquid-liquid interface that is formed between immiscible first and second liquids whereby a polyelectrolyte multilayer film is provided at the liquid-liquid interface. In certain preferred embodiments, the first liquid is an aqueous solution and the second liquid is a liquid crystal. In alternative embodiments, the first liquid is an aqueous solution and the second liquid is an oil. The invention further encompasses polyelectrolyte multilayer films provided by the disclosed methods as well as applications utilizing such materials.