The controlled transfer of organized monolayers of amphiphilic molecules from the air-water interface to a solid substrate was the first molecular-scale technology for the creation of new materials. However, the potential benefits of the technology envisioned by Langmuir and Blodgett in the 1930s have yet to be fully realized. Problems of reproducibility and defects and the lack of basic understanding of the packing of complex molecules in thin films have continued to thwart practical applications of Langmuir-Blodgett films and devices made from such films. However, modern high-resolution x-ray diffraction and scanning probe microscopy have proven to be ideal tools to resolve many of the basic questions involving thin organic films. Here, studies are presented of molecular order and organization in thin films of fatty acid salts, the prototypical system of Katharine Blodgett. Even these relatively simple systems present liquid, hexatic, and crystalline order; van der Waals and strained layer epitaxy on various substrates; wide variations in crystal symmetry and interfacial area with counterions; modulated superstructures; and coexisting lattice structures. The wide variety of possible structures presents both a challenge and an opportunity for future molecular design of organic thin-film devices.