1-naphthol-2-sulfonic acid and 1-naphthol-4-sulfonic acid were synthesized under the dissolution of 1-naphthol in 2-nitrotoluene with stirring 98.08-90％ sulfuric acid at $5-95^{circ}C$ for 1-5 hours. As the reaction temperatures and the reaction time were raised, the yield of 2-sulfonate was decreased, while that of 4-sulfonate was increased. But we could not observe the tendency to the various reaction concentrations of sulfuric acids. The mixtures of two isomeric 1-naphtholulfonic acids in excess concentrated sulfuric acids was quantitatively determinded by using multicomponent spectrophotomeric analysis method on the basis of the ultraviolet absorption peak of the sulfonic acids. The standard deviation in this method was ${pm};2.6$, and the above method seem to be rapid and accurate.