Sulfate radical (SO4 center dot(-))-based oxidation of nitrophenols (NPs) have been widely studied; however, formation of potentially more toxic polynitroaromatic intermediates has been overlooked. In this contribution, we systematically investigated the degradation of four NPs by a SO4 center dot(-)-based oxidation process. Degradation efficiency of NPs followed the order: 2-nitrophenol (2-NP) > 4-nitrophenol (4-NP) > 2,4-dinitrophenol (2,4-DNP) > 2,6-dinitrophenol (2,6-DNP). HPLC and LC-MS/MS analysis confirmed the formation of 2,4-DNP, 2,6-DNP and 2,4,6-trinitrophenol (2,4,6-TNP) during NPs transformation by SO4 center dot(-), suggesting that both denitration and renitration processes occurred. Nitrogen dioxide radicals (NO2 center dot) and phenoxy radicals are responsible for the formation of polynitrophenols. Coupling products including nitrated biphenyls and diphenyl ethers were also detected, which were proposed to be formed by combinations of resonance-stabilized radicals. Electron spin density and charge density calculation showed that ortho C-ortho C and ortho C-phenolic O were the most likely combination ways responsible for coupling products formation. ECOSAR program predicted that polynitrated diphenyl ethers and biphenyls had higher ecotoxicological effects on aquatic species such as fish and daphnia. Therefore, the formation of toxic polynitroaromatic intermediates in SO4 center dot(-)-based advanced oxidation processes should be scrutinized before this technology can be safely utilized for water and wastewater treatment.