The effect of solvent and temperature on the extraction of two polychlorinated biphenyls (PCBs) and five polychlorinated dibenzodioxins (PCDDs) from fly ash is investigated and the variations in recoveries of these analytes are explained. The extraction is performed using chromatographic elution, ultrasound-assisted extraction (UAE), enhanced-fluidity liquid extraction (EFLE), and pressurized fluid extraction (PFE). In each of the extraction methods used, only the use of isopropanol-toluene mixtures (5:95 or 10:90, v/v) shows higher recoveries than the use of toluene alone. Applied temperature is an important factor for the higher recoveries throughout all the extraction methods. After each extraction, chromatographic interferences are removed through a multilayer silica gel column clean-up. The quantification of PCBs and PCDDs is performed using HPLC-UV.