Here we report, for the first time, a modified arc-discharge method for synthesis of Cu/Ag core/shell particles with an Ag shell thickness of about 5 nm, based on the difference in the melting points and the evaporating pressures of the elements Cu and Ag. The present approach can as well provide wider application to synthesis of other core/shell structures with high melting-point metal elements as core and low melting-point metals as shell.