The efficiency of Microwave Assisted Solvent Extraction (MASE) for the simultaneous determination of nonylphenol (NP) and nonylphenol ethoxylates (NPE) in river sediments has been evaluated. An optimisation study was carried out in order to identify the variables having the greatest influence on the extraction efficiency. The comparison between the solvents (methanol and acetone-hexane 1:1) shows that the more polar solvent (i.e. methanol) allows a more effective extraction of NP and NPE from sediments. Analytical results show that there is not a considerable improvement by doubling extraction time, while the increase of solvent volume is significant. The comparative study with Soxhlet and pressurised liquid extraction (PLE) methods demonstrates that Microwave Assisted Solvent Extraction is a suitable alternative extraction method for the 4-NP and 4-NPE determination in river sediments, showing an accuracy and precision comparable to those obtained with PLE and better than those obtained with Soxhlet.