A significant number of polycyclic aromatic hydrocarbon (PAH) extraction methods exists. While studying new reference materials, accelerated solvent extraction (ASE) with the use of a dichloromethane-acetone mixture turned out to be the best extraction method for six selected compounds representing the PAH group. This method allowed the recovery ranging from 90 to 115% and repeatability varying from 0.74 to 1.6. In order to validate the PAH extraction and determination method, liquid chromatography with a fluorescence detector (HPLC/FLD) and gas chromatography-mass spectrometry (GC/MS) were applied. The combination of the two methods enabled the achievement of satisfactory results both in soil being the matrix for the new material and in a new Polish candidate for a reference material. The development and validation of the method for PAH extraction and determination in soil was necessary for the purposes of further certification tests aimed at designating the certified value of the new reference material.