The solubilities of sodium 1- and 2-naphthalenesulfonate (1- and 2-SNS) in aqueous sodium hydroxide solutions were measured over the temperature range from 276 to 337 K at atmospheric pressure by a dynamic method. The experimental results showed that the solubilities of 1- and 2-SNS both increased with temperature and decreased with concentrations of aqueous sodium hydroxide solutions. The experimental data were correlated with the new electrolyte nonrandom two-liquid (ENRTL) model. The calculated results showed good agreement with the experimental data. A new strategy, based on the solubility difference between 1- and 2-SNS in aqueous sodium hydroxide solutions, was carried out in laboratory scale. This new strategy, in which the current process of blowing naphthalene was replaced by removing the 'byproduct according to the solubility difference, overcame the drawbacks of blowing naphthalene and made a good separation effect. The best separation effect was attained when the concentration of aqueous sodium hydroxide solution was 0.07 and the operating temperature was 298.15 K. The purities of obtained 1- and 2-SNS were 0.8369 and 0.9854 in this operating condition, respectively. The new strategy has potential in industrial application for optimizing the production of 2-naphthol.