Bombyx mori silk fibroin is of practical interest for its excellent intrinsic properties utilizable in the biotechnological and biomedical fields. Here, the silk fibroin films were pretreated with different methods and then used as the template for the hydroxyapatite (HA) crystal growth. To study the effect of silk films' surface structure on the protein biomineralization, the films were immersed into 1.5 times simulated body fluid (1.5 x SBF) to induce the HA deposition at 37 degrees C. The results showed that an anisotropic growth of HA crystals was observed on the different films as judging from XRD, TEM and HRTEM data. This was thought that the positions and density of carboxyl groups, C = O and amino groups on the surface of SF films may be different, which play the key effect on HA crystal growth. (C) 2008 Elsevier B. V. All rights reserved.