In the present study, we report a facile method to fabricate polyelectrolyte based core-shell nanofibers with the assistance of the high gradient electric potential between the tip of capillary and the collector. The core-shell structure and the composition of each layer have been supported by TEM and XPS studies. The effect of the electric field on the phase separation was considered to be the major factor. An electric field experiment was introduced to elucidate the influence of electric field on the phase separation process. It was assumed the polyelectrolyte based core-shell nanofibers membrane could be applied in wound care and tissue engineering. Published by Elsevier Ltd.