Spider silk exhibits remarkable properties, especially its well-known tensile performances. They rely on a complex nanostructured hierarchical organization that researches progressively elucidate. Spider silk encompasses a vast range of fibers that exhibit diverse and captivating physical and biological characteristics. The full understanding of the relation between structure and properties may lead in the future to the design of a variety of high-performance, tailored materials and devices. Reknown for being produced in mild and begnin conditions, this outstanding biological material constitutes one the more representative example of biomimetism. In addition, silk's structure is produced with limited means, i.e. low energy and relatively simple renewable constituents (silk proteins). Then, if successfully controlled and adequately transposed in biomaterials, some properties of natural silk could lead to innovative green materials that may contribute to reduce the ecological footprint of societies. In fact, striking recent advanced applications made with B. mori silk suggest that spider silk-based materials may lead to advanced resistant and functional materials, then becoming among the most promising subject of study in material science. However, several challenges have to be overcome, especially our ability to produce native-like silk, to control biomaterials' structure and properties, and to minimize their ecological footprint. This paper reviews the characteristics of spider silk that make it so attractive and that may (or may not) contribute to reduce ecological footprint of materials and the challenges in producing innovative spider silk-based materials. First, from a biomimetic perspective, the structure and models that explain the tensile resistance of natural silk are presented, followed by the state of knowledge regarding natural silk spinning process and synthetic production methods. Biocompatibility (biosafety and biofunctionality) as well as biodegradability issues are then addressed. Finally, examples of applications are reviewed. Features that may lead to the design of green materials are emphasized throughout.