Current commercial products using silk fibroin are primarily fibers, textiles, and some coatings. Novel approaches to processing silk proteins can be used to produce a number of biopolymer-based materials. Silk-based biopolymer materials are easy to envision as new classes, types, and formats of biomaterials in high value biomedical applications. However it is possible to work with the structure and physical chemistry of silks to produce other types of novel materials for other high value applications, including applications tangential to the biomedical sphere. We have discovered that the chemical structure and sequence complexity of silk fiber proteins lend themselves to a variety of “smart” materials formats based on the natural propensity of silks to form chiral liquid crystals in solution. Using processes informed by chiral liquid crystalline phase behavior and by the molecular phase behavior of silk fiber proteins, we have developed a number of highly structured materials. These include materials with periodic chiral nanostructures, useful as chiral molecular sieves, to purify pharmaceuticals. (I would like to acknowledge collaborators H-J Jin, C. Craig, and D. Gyure.)