Lithium plating/stripping was investigated under constant current mode using a copper powder electrode in a super-concentrated electrolyte of lithium bis(fluorosulfonyl)amide (LiFSA) with methylphenylamino-di(trifluoroethyl) phosphate (PNMePh) and vinylene carbonate (VC) as additives. Typical Li plating/stripping for Cu electrodes in organic electrolytes of conventional lithium batteries proceeds at potentials of several millivolts versus a Li counter electrode. In contrast, a large overpotential of hundreds of millivolts was observed for Li plating/stripping with the super-concentrated electrolyte. When Li stripping started immediately after Li plating and with no rest time between plating and stripping, two potential plateaus, i.e., two-step Li stripping, was observed. The potential plateau for the 1^st stripping step appeared at −0.2 V versus a Li metal counter electrode. The electrical capacity for the 1^st stripping step was 0.04 mA h cm⁻², which indicates irregular Li stripping. Two-step Li stripping was also recorded using cyclic voltammetry. The electrochemical impedance spectroscopy (EIS) studies indicated that the two-step Li stripping behaviour reflected two different solid electrolyte interphases (SEIs) on electrodeposited Li in a Cu electrode. The SEI for the 1^st-step stripping was in a transition period of the SEI formation. The open circuit voltage (OCV) relaxation with an order of tens of hours was detected after Li plating and before Li stripping. The in operando EIS study suggested a decrease of the charge transfer resistance in the Cu powder electrode during the OCV relaxation. Since the capacitance for the voltage relaxation was a dozen microfarads, it had a slight contribution to the 1^st-step Li stripping behaviour. The voltage relaxation indicated the possibility that it is difficult for Li ions to be electrodeposited or that the Li plating is in a quasi-stable state.