The invention relates to the technical field of preparation of a modified naphthalene-based superplasticizer, in particular to a method for preparing the modified naphthalene-based superplasticizer from heavy fraction obtained in production process of ethyl alcohol. The method includes the steps of firstly, adding crude naphthalene into a four-neck flask, heating until crude naphthalene is moltencompletely, stirring while adding industrial concentrated sulfuric acid dropwise, and then holding the temperature and detecting the pH value; secondly, cooling to a certain temperature, replenishinga proper quantity of water according to the pH value, performing hydrolysis, after that, adding rectified heavy fraction with stirring; thirdly, adding formaldehyde solution dropwise after finishing stirring, holding the temperature for a while, and then adding alkali liquor slowly to regulate the pH value. The method solves the problems of complex recovery, treatment difficulty, high energy consumption, high cost and the like of heavy fraction generated in the rectification of ethyl alcohol. In the process of condensation, the naphthalene-based superplasticizer is grafted, number and type ofbranches of the naphthalene-based superplasticizer are both increased, and water-reducing rate of concrete can be increased while slump effect can be improved.