As the predominant precursor for high-performance carbon fiber manufacturing, the fabrication of polyacrylonitrile (PAN)-based composite fibers attracts great interest. Ionic liquids (ILs) have recently been investigated for melt-spinning of ultrafine PAN fibers. The plasticizing properties of ILs are significantly affected by the structure of ILs and can be influenced by electronegativity, steric effects, etc. Herein, we report a facile strategy to control the elasticity of the PAN/ILs fibers by tuning the anion structure of ILs. Particularly, the ILs containing nitrile-rich groups exhibited enhanced plasticizing effect and nucleating ability on dissolving PAN components, achieving highly stretchable PAN/ILs fibers.