Different from the traditional method for fabricating core-shell structure nanofiber, the PAN/PDMS nanofibers with core-shell structure (PAN as the core layer and PDMS as the shell layer) have been illustrated, which combines with the synchronous photopolymerization during emulsion electrospinning process. The morphology and structure of as-fabricated PAN/PDMS nanofibers are characterized by SEM and TEM. The composition of PAN/PDMS nanofibers is characterized by FTIR, XPS, TG, and DTG, successfully. The photopolymerization process is characterized by UV-vis spectroscopy indirectly. The WCA tests show that it has good hydrophobicity, which makes it possible as functional material. Meanwhile, the most important thing is that the method provides a flexible design strategy of core-shell structure nanofibers. (C) 2017 Elsevier B.V. All rights reserved.