The review systematizes data on various extraction techniques for sample preparation in the determination of polycyclic aromatic hydrocarbons (PAHs) in environmental samples, provides a classification, and describes the capabilities of these techniques. The main versions and methods of solid-phase extraction (SPE) and liquid-liquid (LLE) extraction of structurally different PAHs from complex multicomponent systems are discussed. The variety of SPE and LLE methods, the peculiarities of their combinations with other methods, and the advantages and disadvantages of each sample preparation method are demonstrated. Chromatographic methods are preferred for detection after the solid-phase or liquid-liquid extraction of PAHs from environmental samples.