The ubiquitous presence of alkylphenol ethoxylates in the environment as well as concern for endocrine disruption effects in biota caused by their degradation products (such as octyl- and nonylphenol) has raised interest in the environmental fate of these compounds. As part of an effort to model their behavior in a subestuary of the Chesapeake Bay, a quantitative method for the analysis of octyl- and nonylphenol, and their ethoxylates (1−5) in water and sediment was developed. Extraction procedures are based on solid-phase extraction techniques. Identification and quantitation of the analytes is done by liquid chromatography coupled to tandem mass spectrometry. Instrument detection limits for the compounds ranged from 0.1 to 9 pg injected on column, which allowed method detection limits of 0.04−3 ng/L in water and 0.2−13 ng/g of dry weight in sediment. The method was used to analyze water and sediment from the Back River, MD, where concentrations for the individual compounds ranged from <8 to 200 ng/L in water and <9 to 6700 ng/g of dry weight in sediment. Additionally, structural information obtained in the mass spectrometer is presented that supports previous observations that nonylphenol and its ethoxylates are composed mainly of isomers with a tertiary α-carbon.