Antheraea pernyi silk fibroin (ASF) solution was prepared by dissolving Antheraea pernyi silk fiber in lithium thiocyanate solution. The ASF/1,4-butanediol (ASF/BDO) blend porous materials were prepared with freeze-drying method. The structure of ASF was investigated by the X-ray diffraction method. The result showed that the structure of regenerated ASF scaffold was α-helix and random coil conformation. After ASF mixed with 5 wt% BDO, the structure of ASF was changed to β-sheet and the ASF scaffolds became water-insoluble. There were some small pores and fibrous structure in the big pores and the surface of pores was rough with a great many raised particles. The scaffolds with the average pore size of 300-1000μm and the porosity of 82-92% can efficiently be produced in this paper. Due to avoid the use of organic solvents or harsh chemicals, these new ASF based porous materials provide much more excellent biocompatibility and is expected to be applied to tissue regeneration scaffolds.