Spider silk is one of the toughest materials known. A spider produces this amazing material from an aqueous spinning dope at ambient temperature and pressure. Spiders produce a range of different silks with varying mechanical and physical properties. We have been utilizing a combination of magnetic resonance techniques to understand the molecular structure of the proteins that comprise the silks and further, to characterize the silk producing process as a whole. It is our belief that a better molecular-level understanding of the proteins’ structure and biochemical processing conditions utilized to assemble the silk fiber will lead to a route for synthetic spider silk production.