In order to seek a natural protein biomaterial alternative with enough mechanical strength for developing demands of biomedical materials, silk fibroin is under reviewed due to its growing attention in biomedicine. Silk fibroin is an insoluble protein produced by the larvae of Bombyx mori, spiders, and other insects. Remarkable properties such as biocompatibility, biodegradable, oxygen and water vapor permeability, and excellent mechanical strength make silk fibroin an ideal biomaterial for biomedical applications. This paper firstly elaborates the chemistry, structure and these unique properties of silk fibroin, and then reviews different silk fibroin-based biomaterials used in biomedicine including hydrogels, nanoparticles, nanofibers, films and scaffolds follow by several emerging advanced silk fibroin-based biomedical products such as micro-needles, implantable electronic devices, resorbable screws and plates.