A sulfurous compound such as a sulfur-rich “float” (concentrate) obtained by flotation of the residue from the leaching of a zinc concentrate is heated at a temperature not lower than the melting point of sulfur but below its boiling point, preferably not higher than 200° C., more preferably not higher than 140° C., and the evolving gas containing sulfur vapor is cooled at a temperature less than the melting point of sulfur, preferably at ordinary temperature, to condense sulfur.