Recently introduced solid-phase microextraction (SPME) method has been applied to many different applications including analysis of air, water, and soil, both organic and inorganic target analytes. Several new devices based on SPME were developed to facilitate the application for air monitoring, integrated sampling, fast gas chromatography, solid-phase microextraction coupled to high-performance liquid chromatography, on-line screening systems, and automation of the entire sample preparation apparatus. This paper discusses recently published SPME methods in this field to outline the high potential of this unique microsampling technique. In addition, solid-phase microextraction is compared to classical sample preparation methods to demonstrate the advantages of this micro technique and new application fields of this technique.