N-nitrosodimethylamine (NDMA) has aroused extensive concern as a disinfection byproduct due to its high toxicity and elevated concentration levels in water sources. This study investigates the photoreductive decomposition of NDMA by UV/iodide process. The results showed that this process is an effective strategy for the treatment of NDMA with 99.2% NDMA removed within 10 min. The depletion of NDMA by UV/iodide process obeyed pseudo-first-order kinetics with a rate constant (k(1)) of 0.60 +/- 0.03 min(-1). Hydrated electrons (e(aq)(-)) generated by the UV irradiation of iodide were proven to play a critical role. Dimethylamine (DMA) and nitrite (NO2-) were formed as the main intermediate products, which completely converted to formate (HCOO-), ammonium (NH4+) and nitrogen (N-2). Therefore, not only the high efficiencies in NDMA destruction, but the elimination of toxic intermediates make UV/iodide process advantageous. A photoreduction mechanism was proposed: NDMA initially absorbed photons to a photoexcited state, and underwent a cleavage of N-NO bond under the attack of eaq-. The solution pH had little impact on NDMA removal. However, alkaline conditions were more favorable for the elimination of DMA and NO2-, thus effectively reducing the secondary pollution. (C) 2016 Elsevier B.V. All rights reserved.