A new methodology, based on the use of accelerated solvent extraction (ASE) and highly selective cleanup using restricted access material (RAM) on-line coupled with liquid chromatography-mass spectrometry (LC-MS), is presented for the simultaneous and unequivocal determination of alkylphenol ethoxylates (APEOs), their degradation products and halogenated derivatives, and steroid sex hormones in sediment samples. Using the integrated RAM-LC-MS system, the simultaneous determination of alkylphenolic compounds and sex hormones was achieved, yielding recoveries higher than 60% and producing low MS background noise.