The application of graphene in catalytic field is getting more and more attention. In present paper, the system of naphthalene - tert-butyl hydroperoxide (TBHP) - graphene oxide was constructed and the effect of graphene oxide (GO) on the oxidation process of naphthalene was studied in detail. The effects of graphene oxide species, types of solvent, oxidant content, the amount of graphene oxide, reaction temperature and reaction time on the oxidation of naphthalene were investigated. The results showed that graphene oxide can improve the conversion of naphthalene and the yield of 1,4-naphthoquinone. Optimum results were achieved when the amount of naphthalene was 100 mg, oxidant (TBHP) 2.4 mL, graphene oxide RGO (10 wt%) 20 mg, reaction solvent acetic acid (1.2 mL), the reaction temperature 100 ℃, reaction time 22 h . On the basis of results obtained, the mechanism of oxidation process of naphthalene in the presence of GO was discussed.