Vitamin E is widely used in personal care and cosmetic products because of its potent antioxidant ability. However, most forms of vitamin E are fat-soluble, which limits the bio-availability of the vitamin E. In this study, electrospun silk fibroin (SF) nanofibers were fabricated as carriers for delivery of a water-soluble derivative of vitamin E (TPGS). Comparing with the pure silk solution, the surface tension of SF/vitamin E mixture sightly decreased, which makes the electrospinning process more smoothly. The fabricated fibers were then treated with 75% ethanol vapor and then immersed in the acetate buffer for 4 days, the morphology of the vitamin E loaded SF nanofibers observed by scanning electronic microscope (SEM) showed no obvious change. Meanwhile, Fourier Transform Infrared (FTIR) spectra demonstrated that the conformation of silk fibroin transformed from silk I form to silk II form. Therefore, electrospun vitamin E loaded nanofiber mats appear to be a promising biomaterial for skin care, wound dressing and skin tissue engineering.