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Melatonin (N‐acetyl‐5‐methoxytryptamine) is an important biological hormone in many abiotic stress responses and developmental processes. In this study, the protective roles of melatonin were investigated by measuring the antioxidant defense system and photosynthetic characteristics in maize under salt stress. The results indicated that NaCl treatment led to the decrease in plant growth, chlorophyll contents and photochemical activity of photosystem II (PSII). However, the levels of reactive oxygen species increased significantly under salt stress. Meanwhile, we found that application of exogenous melatonin alleviated reactive oxygen species burst and protected the photosynthetic activity in maize seedlings under salt stress through the activation of antioxidant enzymes. In addition, 100 μM melatonin‐treated plants showed high photosynthetic efficiency and salinity. Immunoblotting analysis of PSII proteins showed that melatonin application alleviated the decline of 34 kDa PSII reaction center protein (D1) and the increase of PSII subunit S protein. Taken together, our study promotes more comprehensive understanding in the protective effects of exogenous melatonin in maize under salt stress, and it may be involved in activation of antioxidant enzymes and regulation of PSII proteins.