Electrospinning offers an attractive opportunity for producing silk fibroin (SF) nano/micro fibrous scaffolds with potential for tissue regeneration and repair. Electrospun scaffolds of silk fibroin were fabricated as a biomimetic scaffold for tissue engineering. The morphology of the electrospun scaffolds was investigated with SEM and AFM. The SEM images indicated that electrospun SF fibers were ribbon-shaped and the average width increased with increasing SF concentrations. The AFM images revealed that, after treated with methanol, there was a groove on the surface of fiber, which is conducive to cell attachment. The structure of electrospun SF fibers was characterized by NMR, WAXD, and DSC. The results displayed that SF in electrospun fibers was present in a random coil conformation, SF conformation transformed from random coil to beta-sheet when treated with methanol. Cell attachment and proliferation studies with pig iliac endothelial cells (PIECs) demonstrated that electrospun SF scaffolds significantly promoted cell attachment and proliferation in comparison with cast SF films. These results suggest electrospun SF scaffolds may be potential candidates for cardiovascular tissue engineering.