This study was aimed to prepare silk fibroin (SF) of Thai silk (Bombyx mori) and cassava starch blend films by solvent evaporation method. The SF solution was firstly prepared from the cocoons by dissolving pure silk fibroin with tertiary solvent system of CaCl2: Ethanol: H2O (1:2:8 by mol). Cassava starch solution could be prepared by boiling at high temperature. The mixture of the SF and cassava starch solution was then blended and cast on the polystyrene plates. The obtained films were investigated on their morphology, secondary structures and thermal properties by using SEM, FTIR and thermogravimetry, respectively. The results found that SF blended with starch could be formed the higher ratio of β-sheet. With cross-section images, the blend films showed homogeneously texture. In addition, the blend film gradually increased its thermal properties when the starch blended ratio was increased. In conclusion, the SF/starch blend films could be adjusted their properties by varying the blend ratio.