A novel type of all-natural, biocompatible, and very robust nanoscale freestanding biohybrids are reported. They are obtained by integrating a silk fibroin matrix with functional inorganic nanoplatelets using a spin-assisted layer-by-layer assembly. The organized assembly of the silk fibroin with clay (montmorillonite) nanosheets results in highly transparent nanoscale films with significantly enhanced mechanical properties, including strength, toughness, and elastic modulus, as compared to those for the pristine silk nanomaterials. Moreover, replacing clay nanoplatelets with a highly reflective Langmuir monolayer of densely packed silver nanoplates causes a similar enhancement of the mechanical properties, but in contrast to the materials above, highly reflective, mirror-like, nanoscale flexible films are created. This strategy offers a new perspective for the fabrication of robust all-natural flexible nanocomposites with exceptional mechanical properties important for biomedical applications, such as reinforced tissue engineering. On the other hand, the ability to convert silk-based nanoscale films into mirror-like biocompatible flexible films can be intriguing for prospective photonics and optical exploitation of these nanobiohybrids. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA.