Food products are composed of a complex mixture of natural substances that may be added on intention or developed during the production process. Coumarin is a naturally occurring substance that possesses aromatic and fragrant characteristics and can be found all over the plant kingdom. Different studies have demonstrated chronic toxic effects, particularly hepatotoxicity of coumarin. Therefore, it is necessary to quantify coumarin in various food items particularly alcoholic beverages through precise methods. The very low concentrations of coumarin that are often present in alcoholic beverages and the varied resolution and effectiveness of existing analytical techniques make it difficult to determine coumarin, despite the availability of a variety of analytical techniques. However, in this chapter, various modern analytical techniques used for the assessment of coumarin in distilled beverages such as liquid chromatography combined with different detectors, gas chromatography, capillary electrophoresis, and electrochemical sensors have been discussed with reference to the available literature.