Terephthaloyl chloride (DB)-modified silk fibroin (SF) films were immersed into 1.5 times simulated body fluid (1.5 SBF) to regulate the mineralization of hydroxyapatite (HA) crystals at about 36.5 ℃ for 24 h. UV was used to prove that the new bonds form between the DB and SF. The structure and morphology of the SF/HA were investigated by FTIR, ICP, XRD and SEM. The results showed that the apatite deposited on the matrix of SF mainly was HA. HA was self-assembled on the matrix of SF and formed three-dimensional framework when the weight ratio of DB/SF was 0.30. The content of DB affected the structure and morphology of the apatite composites deposited on the SF films.