A fluorine-substituted ionic liquid based on a pyrrolidinium cation and a bis(fluorosulfonyl)imide anion was synthesized using a facile one-step reaction. The resulting ionic liquid is highly pure and when dissolved with LiFSI, the IL-based electrolyte showed good compatibility both in Li and graphite anodes, and superior voltage stability is demonstrated in a LiNi0.5Mn0.3Co0.2O2 cell.