In the current contribution, the application of the Solid Phase Microextraction (SPME) as a modern sample preparation method was discussed. Based on theoretical and practical aspects of the SPME method, a comparison of extraction efficiency of aromatic hydrocarbons (benzene, toluene, ethylbenzene, m,p-xylene (BTEX)) as testing substances was performed. The various SPME coated fibers: commercial (polydimethylsiloxane - PDMS, polyacrylate - PA) and home-made (etoxy-polydimethylsiloxane - PDES, polyurethaneacrylate, fused silica, and fused silica after etching of hydrogen fluoride acid) were compared in these experiments. The extraction efficiency was displayed as the extracted mass for BTEX after extracting of standard solution with various SPME fibers. The most efficient extraction (adsorption on the fiber surface) is for the etoxy-polydimethylsiloxane-coated fibers after drying at 200°C than for other tested fibers. In addition, the possibility of SPME use (with the new PDES fibers) in the food and natural products analysis (wine, candies, herbs) was discussed. Many advantages, as well as disadvantages of the SPME method are described in detail.