Many emerging materials challenges involve designing interfaces to organize two materials with orthogonal chemical properties (e.g. metals and oxides) in geometries in which one or more dimensions approaches the molecular scale. Controlling synthetic interface structure on this scale is still a significant challenge, in part due to physical properties such as line tension and disjoining pressure that increase in importance at very short length scales. However, biology routinely addresses a related challenge in the lipid bilayer, using precise nanometer-scale hydrophilic/hydrophobic orthogonality to spatially organize and gate processes including ion transport, adhesion, and recognition, using polyfunctional phospholipid building blocks. Conventional standing phases of phospholipids such as those in cell membranes do not directly meet many of the common interfacial patterning requirements for synthetic materials. However, polymerizable amphiphiles can be ordered into lying down or ‘sitting’ phases on layered materials, exposing both heads and tails to the environment. We examine physical consequences of structured amphiphilicity on this scale for a variety of applications.