Over the last years, the human probable carcinogen 1,4-dioxane and alkyl-1,3-dioxanes and dioxolanes have been detected and identified as the cause of several pollution episodes in the Llobregat River (Catalonia, NE Spain) and its aquifer. It is an issue of major concern to study these compounds which are released to the environment by resin manufacturing plants\' spills and wastewater discharges spread along rivers and reach drinking water treatment plants (DWTPs) in order to protect the environment and public health. In this study four seasonal sampling campaigns were carried out over a year to determine the removal efficiency of the dioxanes and dioxolanes at each step of a DWTP including ozonation, granular activated carbon filters, ultrafiltration and reverse osmosis step\'s treatments. Additionally, a weekly sampling monitoring of 1,4-dioxane and alkyl-1,3-dioxanes and dioxolanes in raw water, groundwater and finished water was performed at a DWTP over more than two years. Aqueous odor concentration thresholds (OTCs) were established by the three-alternative forced choice method (3-AFC). Following a previous published methodology, samples were analyzed and results showed that the advanced treatment (Ultrafiltration followed by reverse osmosis) line removes more efficiently 1,4-dioxane, alkyl dioxanes and dioxolanes (80 ± 6% for 1,4-dioxane, 97 ± 7% for 5,5-DMD and 100 ± 0% for 2,5,5-TMD) than the upgraded conventional treatment line (ozonation followed by granular activated carbon filters) (-12 ± 50%, 25 ± 62% and 50 ± 51% respectively), where some desorption processes were eventually observed. From the monitoring study, results suggest that the presence of 1,4-dioxane is not only due to spills, but also from other sources of contamination. Whereas dioxolanes almost completely disappeared in time, 1,4-dioxane\'s concentrations remained low and fluctuant. A background concentration of 1,4-dioxane in surface waters (∼1 μg/L) has been determined with a relevant concentration up to 11.6 μg/L of 1,4-dioxane in groundwater. The perception values for some of the studied compounds were extremely low (few ng/L only), which confirms the relevancy of this group of compounds as malodorous agents in waters.