The invention belongs to the field of organic synthesis, and discloses a method for synthesizing a naphthopyran-2-ketone compound. The method comprises the following step: in the presence of benzoquinone, palladium acetate, 3-(4-methoxyphenyl) thiopropane-1-sodium sulfonate and a solvent, a phenolic compound and butyl acrylate react to obtain the naphthopyran-2-ketone compound carrying out a reaction. The phenolic compound is selected from one of the following structures as shown in the specification, wherein R1 is selected from hydrogen, halogen, alkoxy and ester group, R3 is selected from hydrogen, alkyl, alkoxy, trifluoromethyl, acyl and naphthyl, and R2 is selected from hydrogen or halogen. The reaction conditions are simple and mild, only one catalyst is needed, the use amount of thecatalyst is small and only needs 10 mol%, the reaction starts from olefin carboxylic ester, and therefore the reaction has higher economical efficiency. The reaction has good universality, is suitablefor substrates with different substituents, and has high yield.