The presence and longitudinal and temporal distributions of the two main anionic surfactants, linear alkylbenzene sulfonates (LAS) and alkyl ethoxysulfates (AES), were monitored in surface sediments from the Guadalete estuary, located in the north of the Bay of Cadiz (SW of Spain). Seasonal samplings were performed for two years at three different stations; one of them located up-stream near the discharge outlet of a wastewater treatment plant (WWTP). A control station was also sampled in a tidal channel within the boundaries of a natural park adjacent to the estuary. LAS and AES concentration values ranged from 196 to 2864 ng g-1 and from 147 to 557 ng g-1, respectively, the lowest values corresponding to the control station and the highest ones found near the WWTP outlet. A general decrease in the concentrations of both surfactants was found in summer, when degradation processes are faster, whereas the highest concentrations were detected during the wet months, when temperature decreases and rainwater exceeds the WWTP capacity, so untreated wastewater is discharged directly into the river. Due to differential sorption and degradation processes, the relative distribution of LAS homologues in sediments showed higher percentages for those having longer alkyl chains, whereas AES homologues with an even carbon unit number in the alkyl chain and AES ethoxymers with fewer ethylene groups were predominant. No hazard for aquatic organisms was foreseen at the concentrations found for both surfactants along the estuary.