The invention relates to a purification method of 1-nitroso-2-naphthol. The method comprises the following steps of 1, mixing 1-nitroso-2-naphthol (coarse products) with a structure formula shown as acompound (II) with an addition reagent and a solvent-1; performing stirring under the room temperature condition until the reaction is completed; obtaining addition products; 2, mixing the addition products with the solvents 2; adding alkali under the room temperature and stirring conditions to obtain 1-nitroso-2-naphthol (fine product) with the structure formula shown as a compound (II). The formulas are shown in the description. The invention discloses a purification method of an organic compound with nitroso groups in a molecular structure. Concretely, the 1-nitroso-2-naphthol (coarse products) and the sodium hydrogen sulfite (or similar substances) are subjected to addition reaction to obtain addition products; the addition products and alkali react to obtain the 1-nitroso-2-naphtholfine product with the purity being not less than 99 percent. By using the method provided by the invention, the product yield is high; the operation is convenient and fast; the industrialization is easy.