The photoconversion of 2-chloronaphthalene (CN-2) in water in a simulated sunlight system was investigated. The photoconversion efficiency, photoproducts and mechanisms were inspected, and the effects of inorganic ions (NO, NO) and fulvic acid (FA) were discussed. The results showed that CN-2 could be transformed in water under the irradiation. NO and NO promoted the photoconversion of CN-2 owing to ·OH generated by the photolysis of NO and NO; FA at a lower concentration promoted the photoconversion, but it had an inhibition effect at a higher concentration. It was demonstrated that the acidic conditions promoted the photoconversion of CN-2 by the active groups such as superoxide radical anion, hydrogen peroxide and hydroxyl radical produced in the system. Eight photoproducts of CN-2 were characterized by the GC-MS method and the possible photoconversion mechanisms were proposed accordingly.