N-methyl-N-allylpyrrolidinium bis (trifluoromethanesulfonyl) imide (PYR1ATFSI) with substantial supercooling behavior is synthesized to develop low temperature electrolyte for lithium-ion batteries. Additive fluoroethylene carbonate (FEC) in LiTFSI/PYR1ATFSI/EC/PC/EMC is found that it can reduce the freezing point. LiFePO4/Li coin cells with the FEC-PYR1ATFSI electrolyte exhibit good capacity retention, reversible cycling behavior at low temperatures. The good performance can be attributed to the decrease in the freezing point and the polarization of the composite electrolyte.