Single drop microextraction (SDME) nowadays earns an increasing attention by scientists due to its simplicity, low cost and the need for only common laboratory equipment. This microextraction technique combines sample cleanup and pre-concentration of analytes in one step. Furthermore, a significant reduction in the amount of organic solvents needed comparing to standard LLE techniques places SDME into the position of environmental friendly extraction techniques. SDME is a straightforward technique in which a micro-drop of solvent is suspended from the tip of a conventional micro-syringe and then it is in a direct contact with a sample solution in which it is immiscible or it could be suspended in the headspace above the sample. The paper overviews developments of the state-of-the-art SDME techniques for the extraction of harmful organic compound and pollutants from environmental, food and biological matrices. Key extraction parameters essential for SDME performance were described and discussed.