N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr1,2O1TFSI)-based electrolyte is used in Li/S cells, and a series of electrolyte with binary Pyr1,2O1TFSI-1,3-dioxolane (DOL) or Pyr1,2O1TFSI-1,2-dimethoxyethane (DME) solvent is investigated, and bis(fluorosulfonyl)imide lithium (LiFSI) is further used as the additive. The effect of Pyr1,2O1TFSI is studied in terms of scanning electron microscopy (SEM), UV-visible absorption spectroscopy (UV) as well as electrochemical measurement. The results show that using 1molkg−1 bis(trifluoromethanesulfonyl)imide lithium (LiTFSI)/Pyr1,2O1TFSI-DOL (65:35w/w) with 1wt % LiFSI electrolyte leads to the most stable cycling and decent capacity performance, along with high coulombic efficiency.