Charge-discharge behavior of Li and Li-Al anodes has been investigated by measurement of AC impedance and polarization resistance. The anodes showed lower interfacial resistance in ethylene carbonate (EC)-dimethyl carbonate (DMC)/1 M LiPF6 than that in EC-diethyl carbonate (DEC)/1 M LiPF6. The interfacial resistance between Li-Al electrode and electrolyte solution decreased with content of Al in the alloy. Further, addition of 2-methylfuran (2MeF), 2-methyltetrahydrofuran (2MeTHF), 2-methylthiophene (2MeTp) and polyethylene oxide (PEO) in the electrolyte solutions decreased the polarization resistance.