Production of polyelectrolyte fibers via electrospinning is more challenging compared to neutral polymers because of their ionic nature. In this paper, a comprehensive approach to achieve poly(ionic liquid) fibers is presented. We show that small-angle X-ray scattering is a valuable tool to provide a deeper understanding of the structure of the polymer in solution and its relation to spinnability. We found that in dimethylformamide, the poly(ionic liquid) acted like a conventional polyelectrolyte with disassociated ions, and attempts to electrospin it resulted in bead formation. When methanol was added, the polymer structure was more neutral-like and fibers were successfully formed. Thus, tuning the solvent of the electrospinning solution could induce a change in the structure of the polyelectrolytes in the solution to a more neutral structure that favors fiber production. This approach could facilitate the development of future electrospun polyelectrolyte fibers.