In bone tissue engineering, fabrication of scaffold materials that are biodegradable with regenerative functions is one of the most important research fields. Silk fibroin exhibits many favorable characteristics used as scaffold materials. Among them, hybrid silk fibroin/inorganic composites prepared by biomimetic mineralization have better biocompatibility, biomechanical properties, and biodegradability. At the same time, the hybrid silk fibroin/inorganic materials have much better osteoinduction and conduction properties than silk fibroin. Here, the recent advances in the preparation of silk fibroin/silica hybrid materials by combination or biomimetic silicification are reviewed, and the future research prospects of silicification of silk fibroin are discussed.