Considerable effort has been directed toward the use of silk fibroin as a biotechnological material in biomedical applications on account of its excellent biodegradability, biocompatibility, and unique mechanical properties. For use in tissue engineering, it is very important to design and control the pore architecture of polymeric scaffolds, which provide the vital framework for seeded cells to organize into functioning tissue. In the present study, a silk fibroin scaffold with controlled interconnectivity and pore size was prepared using an electrospinning method with poly(ethylene oxide).