Langmuir-Blodgett (LB) films occupy a unique niche at the crossroads of materials science, complex fluids, and biophysics. They have many similarities to inorganic epitaxial films due to the layer by layer deposition process; however, the amphiphilic nature of the constituent molecules provides the connection to lyotropic liquid crystals and membranes. A great deal is known about LB film structure and thermodynamic behavior; both from classical studies as well as from recent experiments using sophisticated characterization techniques such as synchrotron X-ray scattering and scanning probe microscopy. This article summarizes the current understanding of these systems from a physical/structural point of view. Included are discussions of the deposition process, the layered nature of LB films, intralayer molecular packing, defects, stability, and phase transitions.