Single drop microextraction technique uses microamounts of organic solvents. Simplicity, low cost, low environmental impact, compatibility with chromatographic systems as well as its applicability to different matrices are main advantages of single drop microextraction. This technique has become frequently used for the extraction of a broad scope of compounds for numerous analytical applications. This review provides an overview of the existing single drop microextraction modes of realisation and the main scope is devoted to the optimization of parameters influencing the efficiency. The state of the art is discussed on the basis of examples selected from representative application areas. Extraction parameters for toxic organic compounds extraction and microdrop stability were evaluated.