A simple, efficient matrix solid phase dispersive extraction (MSPD) method was optimised to analyse simultaneously polycyclic aromatic hydrocarbons (PAHs) and polychlorobiphenyls (PCBs) from sediments, and was compared to microwave-assisted extraction (MAE). New dispersing agents were tested to improve MSPD extraction. 3-chloropropyl-bonded silica particles, in addition to Florisil, increased significantly the polyaromatics desorption capacity. A compromise was found for eluting both families of compounds from sediments, using a small volume of hexane/acetone. Low procedural detection limits could be reached (0.06–0.22 ng g−1 and 0.3–1.1 ng g−1 for PAHs and PCBs, respectively). Mean total extraction recoveries were good for PAHs (>67%, depending on the sediment) and for PCBs (>89%), with good precision (6–9% and 4–10% inter-day precision for PAHs and PCBs, respectively). Higher recoveries for PCBs could be reached in comparison with formerly developed sonication or Soxhlet extraction methods, but also with MAE. MSPD offered significant decrease of sample amount, of solvent consumption and allowed more efficient cleaning of the sediment matrix, leading to less matrix effects compared to MAE, removing lots of interfering compounds without additional purification step. The robustness of the MSPD methodology could be demonstrated extracting quantitatively sediments from different sources and with various mineralogical characteristics.