Traditional Chinese medicine has been clinically used in China for many years, with experimental studies and clinical trials having demonstrated that it is safe and valid. Among many traditional natural medicines, Chuanxiong and Asarum have been proven to be effective in the treatment of relieving pain. Actually, as well as analgesic, they have common attributes, such as anti-inflammatory, cardiovascular benefits, and anticancer activities, with volatile oils being their major components. Furthermore, Chuanxiong and Asarum have been combined as drug pairs in the same prescription for thousands of years, with examples being Chuanxiong Chatiao San and Chuanxiongxixintang. More interestingly, their combination has better therapeutic effects on diseases than a single drug. After the combination of Chuanxiong and Asarum forms a blend, a series of changes take place in their chemical components, such as the contents of the main active ingredients, ferulic acid and ligustilide, increased significantly after this progress. At the same time, the pharmacological effects of the combination appearing to be more powerful, such as synergistic analgesic. This review focuses on the chemical constituents and pharmacological activities of Chuanxiong, Asarum, and Chuanxiong Asarum compositions.