A grain-oriented electrical steel sheet being a grain-oriented electrical steel sheet containing Si of 0.8 mass % to 7 mass %, Mn of 0.05 mass % to 1 mass %, B of 0.0005 mass % to 0.0080 mass %, each content of Al, C, N, S, and Se of 0.005 mass % or less, and a balance being composed of Fe and inevitable impurities and having a glass coating film made of composite oxide mainly composed of forsterite on the steel sheet surface, in which when glow discharge optical emission spectrometry (GDS) to the surface of a secondary coating film formed on the surface of the glass coating film under a predetermined condition is performed, a peak, of B, in emission intensity having a peak position in emission intensity different from a peak position, of Mg, in emission intensity is obtained and the peak position, of B, in emission intensity from the steel sheet surface is deeper than the peak position, of Mg, in emission intensity.