Abstract: The invention provides a method of industrially producing high-quality polyethylenepolyamines, which exerts high decolorizing effect and is economical, comprising the steps that hydrogen halide is added to a mixture of polyethylenepolyamines and heated, then distillation is performed to fractionate components each having a boiling point not higher than that of triethylenetetramine, next alkali metal hydroxide is added to that residual liquor after distillation to neutralize, and distillation is performed again to fractionate components each having a boiling point not lower than that of tetraethylenepentamine.