Spain is one of the European countries that still discharges untreated wastewaters and sewage sludge to the sea. A total of 35 samples of coastal waters and 39 samples of harbor sediments was analyzed. Samples were collected from several hot spots on the Spanish coast, such as the harbors of Tarragona, Almería, and Barcelona, the mouths of the Besos and Llobregat rivers, the Bay of Cadiz, and various yacht harbors at the Mediterranean coast. A generic analytical procedure based on solid-phase extraction-liquid chromatography-atmospheric pressure chemical ionization/electrospray ionization mass spectrometry (SPE-LC-APCI/ESI-MS) was employed for determining the concentrations of alcohol ethoxylates (AEO), nonylphenol ethoxylates (NPEO), coconut diethanol amides (CDEA), nonylphenoxy-monocarboxylates (NPEC), nonylphenol (NP), octylphenol (OP), and linear alkylbenzene sulfonates (LAS) in sediment and water samples. The analysis revealed the presence of considerably high concentrations of NPEOs and NP near the points of discharge of industrial and urban wastewaters. Nonylphenol was found in 47% of water samples and in 77% of all sediment samples analyzed. Values for NP ranged from <0.15 to 4.1 microg/L in seawater and from <8 to 1,050 microg/kg in sediments. Levels of AEOs and CDEAs in seawater and marine sediments are reported for the first time. Concentrations of CDEAs in sediment, which were predominated by C11 through C15 homologues, ranged from 30 to 2,700 microg/kg, while in seawater, concentrations found were up to 24 microg/L. The AEOs were found to accumulate in a bottom sediment and they were detected in all analyzed sediment samples in concentrations from 37 to 1,300 microg/kg.