Highly sensitive detection of refractive index (RI) is essential for the analysis of the bio-microenvironment and basic cellular reactions. To achieve this, optic-fiber RI sensors based on localized surface plasmon resonance (LSPR) have been widely used for their flexibility and high sensitivity. However, the current optic-fiber RI sensors are mainly fabricated using glass, which makes them face the challenges in biocompatibility and biosafety. In this work, a RI sensor with high sensitivity is fabricated using metal-nanostructure-decorated spider silk. The spider silk, which is directly dragged from , is natural protein-based biopolymer with low attenuation, good biocompatibility and biodegradability, large RI, great flexibility, and easy functionalization. Hence, the spider silk can be an ideal alternative to glass for sensing in biological environments with a wide RI range. Different kinds of metal nanostructures, such as gold nanorods (GNRs), gold nanobipyramids (GNBP), and Ag@GNRs, are decorated on the surface of the spider silk utilizing the surface viscidity of the silk. By directing a beam of white light into the spider silk, the LSPR of the metal nanostructures was excited and a highly sensitive RI sensing (the highest sensitivity of 1746 nm per refractive index was achieved on the GNBP-decorated spider silk) was obtained. This work may pave a new way to precise and sensitive biosensing and bioanalysis.