Baicalin is one of the major bioactive components of Scutellaria radix, a Chinese herb that has been used since ancient times. Baicalin has various pharmacological activities, including antitumor, antimicrobial, and antioxidant, and has wide clinical applications. Baicalin displays a distinct pharmacokinetic profile including gastrointestinal hydrolysis, enterohepatic recycling, carrier-mediated transport, and complicated metabolism. The in vivo disposition of baicalin is affected by combinations of other herbs and baicalin can interact with other co-administered drugs due to competition between metabolic enzymes and protein binding. Furthermore, baicalin exhibits altered pharmacokinetic properties under different pathological conditions. Due to its low bioavailability, emerging novel baicalin preparations including nano/micro-scale baicalin delivery systems show better absorption and higher bioavailability in preclinical studies, and show promise for future clinical applications. Thus, this current review offers a comprehensive report on the pharmacokinetic behavior of baicalin and strategies to improve its bioavailability.