N-nitrosodimethylamine (NDMA), as an emerging nitrogenous disinfection byproduct, is strictly controlled by multiple countries due to its high toxicity in drinking water. Advanced reduction processes (ARPs) are a new type of water treatment technology that can generate highly reactive reducing radicals and make environmental contaminants degrade rapidly and innocuously. In this study, a systematic investigation on the kinetics of the NDMA degradation via the chosen UV/sulfite ARP and the impacts of some key parameters of reaction system was conducted. The results indicated that the UV/sulfite ARP was an efficient and energy saving method for the reductive degradation of NDMA. A total of 94.40% of NDMA was removed using the UV/sulfite ARP, while only 45.48% of NDMA was removed via direct UV photolysis under the same reaction conditions. The degradation of NDMA via the UV/sulfite ARP followed pseudo-first-order kinetics. Increasing both the UV light intensity and sulfite dosage led to a proportional increase in the NDMA removal efficiency. The alkaline condition favored the degradation of NDMA, with the removal efficiency increasing from 21.57% to 66.79% within the initial 5 min of the reaction when the pH increased from 3 to 11. The presence of dissolved oxygen substantially decreased the removal efficiency of NDMA due to the formation of oxidizing superoxide radicals, which competed with NDMA by capturing the reducing active radicals during the reaction. An analysis of the degradation products indicated that several refractory intermediates such as dimethylamine, methylamine and nitrite were completely decomposed via the UV/sulfite ARP, and the final degradation products were formate, ammonia and nitrogen.