• Pericarp browning of longan after harvest is linked to RNS and nitrosative stress. • ClO 2 treatment inhibits RNS generation and relieve nitrosative stress. • ClO 2 reduces activities of RNS producing enzymes (NOS and NR) and maintains their substrates in longan pericarp. • ClO 2 fumigation reduces pericarp browning in postharvest longan during storage by modulation of nitrosative stress. Reactive nitrogen species (RNS) play a crucial role for plants to respond to environmental fluctuations. High formation of RNS leads to nitrosative stress and disorders in the higher plant. The use of gaseous chlorine dioxide (ClO 2 ) treatments for postharvest application has grown in recent years due to its advantages over other methods, including its powerful antibrowning and antimicrobial activities and low environmental impacts. The purpose of this research was to determine the influence of ClO 2 on RNS generation and nitrosative stress associated with browning of longan ( Dimocarpus longan cv. Daw) pericarp after harvest. Longan were harvested and fumigated with ClO 2 (0 and 10 mg L −1 ) for 10 min before being put in cardboard boxes and stored at 25±1°C for 7 d. The findings revealed that rapid pericarp browning was evident in the control at 6 h and the intensity increased steadily during storage. Browning developed in tandem with a significant rise in RNS levels (nitric oxide, nitrogen dioxide, peroxynitrite and S-nitrosoglutathione) and nitrosative stress (S-nitrosothiol, 3-nitrotyrosine, 8-nitroguanine and nitro fatty acid). Nitric oxide producing enzyme activities, including nitric oxide synthase (NOS) and nitrate reductase (NR), increased with a decline in their substrate contents (L-arginine and nitrate) and their product (L-citrulline and nitrite) and pH were also raised during severe pericarp browning. However, ClO 2 fumigation reduced the activities of RNS producing enzymes and maintained their substrates for up to 5-6 d of storage. These reductions were correlated to lower RNS levels, nitrosative stress and pericarp browning, indicating that ClO 2 treatment could diminish postharvest browning of ‘Daw' longan pericarp by lowering the activity of the RNS-producing enzyme, causes a reduction in RNS to counteract nitrosative stress.