Rhenium (Re) is a refractory metal which exhibits an extraordinary combination of properties. Thus, nanowires and other nanostructures of Re-alloys may possess unique properties resulting from both Re chemistry and the nanometer scale, and become attractive for a variety of applications, such as in catalysis, photovoltaic cells, and microelectronics. Rhenium–tin coatings, consisting of nanowires with a core/shell structure, were electrodeposited on copper substrates under galvanostatic or potentiostatic conditions. The effects of bath composition and operating conditions were investigated, and the chemistry and structure of the coatings were studied by a variety of analytical tools. A Re-content as high as 77at.% or a Faradaic efficiency as high as 46% were attained. Ranges of Sn-to-Re in the plating bath, applied current density and applied potential, within which the nanowires could be formed, were determined. A mechanism was suggested, according to which Sn nanowires were first grown on top of Sn micro-particles, and then the Sn nanowires reduced the perrhenate chemically, thus forming a core made of crystalline Sn-rich phase, and a shell made of amorphous Re-rich phase. The absence of mutual solubility of Re and Sn may be the driving force for this phase separation.