Langmuir monolayers at the air/water interface are distinguished by their richness of phases. These can be assigned to smectic categories, although the dominant competing interactions are not yet well elaborated. For single chain compounds, there are van der Waals attractions of the chains and repulsive forces of the head groups competing in determining the local structure. For larger molecules like phospholipids there appear also to be important dipolar interactions of the head groups. In order to study these interactions, we report surface X-ray diffraction studies of films of fatty acids and phospholipids at the air/water interface, with varying environmental parameters, as well as head group size and shape. We observe a wealth of mesophases and also the influence of molecular chirality on the structure. The defined control of the monolayer structure can be made use of to control crystal formation by diffusion from the subphase and nucleation at the interface. This is studied spectroscopically, microscopically andviaelectron diffraction of transferred films of cyanine dyes. In that case one observes epitaxy between the dye crystal and surfactant layer, and the relative lattices can be varied via suitable dye mixtures. A very peculiar interfacial influence results from the orientation of molecular dipoles at the interface. This causes long-range repulsive interactions leading to periodic superlattices in two phase coexistence regions. These forces are observed and quantified via fluorescence microscopy.