Chronic headache such as migraine and nervous headache has become one of the most common locations of pain and one of the most difficult diseases to recover due to its numerous causes and inconvenience to keep acesodyne administration for a long time. However, there are a series of treatment theories and herbal formulas for this disease in traditional Chinese medicine (TCM), in which Da Chuanxiong formula (DCXF), a herb pair composed of Chuanxiong Rhizoma (CR), Chuanxiong in Chinese, and Gastrodiae Rhizoma (GR) called as Tianma in China, is a greatly classic representative. This formula has been used for headaches via dispelling wind pathogen and dissipating blood stasis for many years in TCM. In recent years, the efficiency and representativeness of DCXF have garnered many researchers’ attention. To reveal the compatibility mechanism and develop innovative Chinese herb, herein ethnopharmacological relevance, chemical characters, and pharmacological actions of DCXF are detailed. It is expected to give a comprehensive interpretation of DCXF, namely, Chuanxiong Tianma herb pair (CTHP), to inherit the essence of herb pair and innovate drug delivery system of this prescription.