The behavior of LAS (linear alkylbenzene sulfonate) in different environmental compartments was studied through wastewater treatment process steps in sewage treatment plants of Alicante and Benidorm (activated sludge type) as well as in Guardamar (lagoons). The fate of LAS, using a specific HPLC method, was monitored during treatment sludge compostage and soil amendment operations. Finally, the marine sediments close to a submarine wastewater sewer outfall were analyzed. The results show significant differences between distribution of LAS homologs in water and solids (sludges, sediments, and soils), as compared to the original distribution in detergent formulations, yielding a lower LAS average molecular weight in water samples. The change observed in the homolog distribution of LAS implies a reduction in the toxicity to Daphnia, because a lower average molecular weight of LAS is less toxic.