The electrochemical behavior of the interface between lithium (Li) alloy electrodes containing a small amount of metal [aluminum (Al) or tin (Sn)] and a propylene carbonate (PC)-based electrolyte has been investigated. The contents of Al and Sn were below 3.0wt.%. Ac impedance analysis revealed that Li-Al electrodes showed relatively low and stable resistance at the electrode/electrolyte interface during the electrode immersion in the electrolyte as well as during charge-discharge cycling. On the other hand, a Li-Sn electrode gave higher interfacial resistance than a "pure" Li electrode. Cyclic voltammetry measurement and galvanostatic charge-discharge cycling test revealed the Li-Al electrode exhibited small polarization from the ideal redox potential of Li/Li+ during charging and discharging while the Li-Sn electrode showed relatively large polarization. The polarization behavior of the various electrodes correlated with the interfacial resistance characterized by the ac impedance measurement.