Silks were boiled in an aqueous solution of sodium carbonate to extract the sericin proteins. The extracted silk was dissolved in a limited concentration LiSCN solution and dialyzed in water. Then cast it on polystyrene dish surfaces to make films. The films were carried out in HFIP, and we prepared non-woven web of regenerated Samia Cynthia ricini silk fibroin fibers with electrospinning method. The morphology of the non-woven web were investigated by SEM. The polymeric structure of the electrospun fibers were analyzed by FTIR, X-ray and DTA/TG. The result showed that the diameter of the non-woven web fibers from the regenerated Samia Cynthia ricini silk fibroin were about several micrometers, and the polymeric structure was great different from natural silk fibroin.