The treatment of an actual wastewater from ammunition manufacturing process containing highly hazardous nitramine explosives has been studied by different water treatment technologies based on Fenton's chemistry. The in-situ production of hydroxyl radical as highly oxidizing agent conducted to the overall degradation of the nitramine explosives contained in the effluent samples. The kinetic abatement of octahydro-1,3,5,7-tetranitro1,3,5,7-tetrazocine (HMX) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) followed the crescent order Fenton = photo-Fenton > electro-assisted Fenton process. The greater performance of the electro-assisted process is justified by the faster regeneration of Fe2+ from the electrochemical reduction and the oxidation contribution of the heterogeneous hydroxyl radical electrogenerated on the dimensional stable anode surface. On the other hand, similar DOC abatements of ca. 60% were attained after 2 h of treatment for all the technologies, being slightly superior for the photo-Fenton process due to the photodecarboxylation of carboxylate-iron complexes. The evaluation of the BOD5 and COD allowed considering the effluent biodegradability enhancement after Fenton's technologies treatment, being feasible their application prior to a biological treatment. From the by-products identification, degradative pathways of the main nitramine pollutants contained in the actual effluent have been proposed. (C) 2017 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.