Cycling behavior of lithium in PC(propylene carbonate)-EC(ethylene carbonate)DME(dimethoxyethane) and PC-EC-DMC(dimethylcarbonate)-based electrolytes has been investigated and correlated with electrode morphology and impedance parameters. Better cycling efficiencies have been obtained in PC-EC-DMC mixtures. A higher stability of the lithium-electrolyte interface in these mixtures has been produced through the evolution of film resistances and through the structure of electroplated lithium. Impedance spectroscopy allowed us to study the modification of the lithium-electrolyte interface during cycling. We observed unusual behavior of the interface in LiPF6-based electrolytes involving the formation of an electroactive passivating layer.