Silk fibroin (SF) films containing 5wt% of CaCl2 were prepared by a cast-film method from the degummed SF and then immersed into the simulated body fluid (SBF) to deposit hydroxyapatite (HAp) crystals. The multilayer film of HAp and SF (5-layers), and pure SF film (4-layers) were prepared by a thermo-compression method at 130 °C and 3MPa for 4min. The ratio of β-sheet structure against other structures in both samples showed almost same value of 55.8% and 55.1%. The swelling ratio and in vitro biodegradation were examined by incubating in phosphate-buffered saline (PBS) with and without protease XIV for 1 to 14 days. The changes of sample weight and its tensile strength were investigated. The multilayer film showed slower biodegradation and higher mechanical strength compared with pure SF film.