This work describes current trends in the development of headspace microextraction methods. The main trends in the selection of detection techniques used in combination with microextraction and preferences in the selection of headspace liquid-phase microextraction (HS-LPME) or headspace solid-phase microextraction (HS-SPME) methods, depending on the analytes and their quantity, are also briefly presented. In the main part of the work, on the basis of current journal literature, headspace microextraction analytical methods used for the determination of various inorganic and organic analytes are classified and compared over the last five years. The work also reflects the current modifications of techniques and approaches proposed for these microextraction methods.