Porous silk fibroin materials, with average pore size 10 similar to 300 mum, pore density 1 similar to 2000/mm(2), and porosity 35 similar to 70%, were prepared by freeze drying aqueous solution of silk fibroin obtained by dissolving silk fibroin in ternary solvent CaCl2 . CH3CH2OH . H2O. Pore size distribution of such materials mostly accorded with logarithmic normal distribution. It is possible to control the aforementioned structural parameters and the physical properties of moisture permeability, compressibility, strength, elongation, etc., by adjusting freezing temperature and concentration of silk fibroin solution. Above glass transition zone (-34 similar to -20 degreesC) of silk fibroin, the freezing temperature has more significant effect on the structure and properties of porous silk fibroin materials.