This paper denotes the importance of operational parameters for the feasibility of ozone (O-3) oxidation for the treatment of wastewaters containing 1,4-dioxane. Results show that O-3 process, which has formerly been considered insufficient as a sole treatment for such wastewaters, could be a viable treatment for the degradation of 1,4-dioxane at the adequate operation conditions. The treatment of both synthetic solution of 1,4-dioxane and industrial wastewaters, containing 1,4-dioxane and 2-methyl-1,3-dioxolane (MDO), showed that about 90% of chemical oxygen demand can be removed and almost a total removal of 1,4-dioxane and MDO is reached by O-3 at optimal process conditions. Data from on-line Fourier transform infrared spectroscopy provides a good insight to its different decomposition routes that eventually determine the viability of degrading this toxic and hazardous compound from industrial waters. The degradation at pH > 9 occurs faster through the formation of ethylene glycol as a primary intermediate; whereas the decomposition in acidic conditions (pH <5.7) consists in the formation and slower degradation of ethylene glycol diformate.(C) 2014 Elsevier B.V. All rights reserved.