Baicalin (7-D-glucuronic acid-5,6-dihydroxyflavone) belongs to natural flavonoids extracted from the roots of Scutellaria baicalensis, the plant used in traditional Chinese medicine. It has been proven that baicalin has various pharmacological activities, such as antioxidant, anti-inflammatory, anticancer, antibacterial, and anti-apoptotic ones. However, it is essential not only to determine the medical usefulness of baicalin, but also to find and develop the most effective methods for its extraction and detection. Therefore, the aim of this review was to summarize the current methods of detection and identification of baicalin and to present the medical applications of baicalin and the underlying mechanisms of its action. Based on the review of the latest literature, it can be concluded that liquid chromatography alone or together with mass spectrometry is the most commonly used method for the determination of baicalin. Recently, also new electrochemical methods have been established, e.g., biosensors with fluorescence, which have better detection limits, sensitivity, and selectivity.