A series of imidazolium-based zwitterionic compounds having both a propylsulfonate group at 3-position and an ester group at 1- or 2-position are synthesized and their interactions with LiPF6 are investigated. FT-IR study and theoretical calculation using density functional theory show that the interactions of the zwitterionic compound with LiPF6 varies significantly with the location of the ester group on the imidazolium ring. The electrochemical stability of the imidazolium-based zwitterionic compound is significantly improved by introducing an ester group at the C-2 position of the imidazolium ring. Cycle performance tests show that the initial cell capacity remains almost unchanged up to 100 cycles at 1/2C when 2.5wt.% of 2-(acetoxymethy)-1-butylimidazolium-3-propylsulfonate is added to the model electrolyte consisting of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC) (EC/DMC/EMC=1/1/1 v/v/v), whereas the capacity of the cell containing an unsubstituted or methyl-substituted imidazolium compound at the C-2 position, 1-(acetoxymethyl)imidazolium-3-propylsulfonate or 1-(acetoxymethyl)-2-methylimidazolium-3-propylsulfonate as an additive, starts to decrease rapidly just after a few cycles.