An electrolytic Sn-plated steel sheet comprising: a base steel sheet; and an electrolytic Sn-plated layer which is disposed on the base steel sheet, has a Sn layer and an alloy layer, and contains Sn: 10 to 100 mass%, Fe: 0 to 90 mass%, and O: 0 to 0.5 mass%, wherein the Sn layer exists on the surface side of the electrolytic Sn-plated layer and the alloy layer exists on the base steel sheet side of the electrolytic Sn-plated layer, wherein a Pb content of the whole electrolytic Sn-plated layer is 50 ppm by mass or less, and in a case where a thickness of the electrolytic Sn-plated layer is represented by t and a region from a surface of the electrolytic Sn-plated layer to a depth of (1/10)×t in a sheet thickness direction is defined as a surface layer region, a Pb content of the surface layer region is 5 ppm by mass or greater and 60 ppm by mass or less and the Pb content of the surface layer region is higher than the Pb content of the whole electrolytic Sn-plated layer, wherein the components of the electrolytic Sn-plated layer is analyzed by glow dischargemass spectrometry (GD-MS) analysis, in the GD-MS analysis in the sheet thickness direction of a sample collected from an arbitrary position in the electrolytic Sn-plated steel sheet, a region ranging from the surface to a region having a Sn content of 100,000 ppm or greater is defined as the electrolytic Sn-plated layer while a region wherein no element is detected for several minutes after discharge is not included in the electrolytic Sn-plated layer, in the electrolytic Sn-plated layer, a region where the Sn content is higher than the Fe content is defined as a Sn layer, and in the electrolytic Sn-plated layer, a region other than the Sn layer is defined as an alloy layer (Fe-Sn layer). a base steel sheet; and an electrolytic Sn-plated layer which is disposed on the base steel sheet, has a Sn layer and an alloy layer, and contains Sn: 10 to 100 mass%, Fe: 0 to 90 mass%, and O: 0 to 0.5 mass%, wherein the Sn layer exists on the surface side of the electrolytic Sn-plated layer and the alloy layer exists on the base steel sheet side of the electrolytic Sn-plated layer, wherein a Pb content of the whole electrolytic Sn-plated layer is 50 ppm by mass or less, and in a case where a thickness of the electrolytic Sn-plated layer is represented by t and a region from a surface of the electrolytic Sn-plated layer to a depth of (1/10)×t in a sheet thickness direction is defined as a surface layer region, a Pb content of the surface layer region is 5 ppm by mass or greater and 60 ppm by mass or less and the Pb content of the surface layer region is higher than the Pb content of the whole electrolytic Sn-plated layer, wherein the components of the electrolytic Sn-plated layer is analyzed by glow dischargemass spectrometry (GD-MS) analysis, in the GD-MS analysis in the sheet thickness direction of a sample collected from an arbitrary position in the electrolytic Sn-plated steel sheet, a region ranging from the surface to a region having a Sn content of 100,000 ppm or greater is defined as the electrolytic Sn-plated layer while a region wherein no element is detected for several minutes after discharge is not included in the electrolytic Sn-plated layer, in the electrolytic Sn-plated layer, a region where the Sn content is higher than the Fe content is defined as a Sn layer, and in the electrolytic Sn-plated layer, a region other than the Sn layer is defined as an alloy layer (Fe-Sn layer).