Dao-di herbs have both natural and humanistic attribute. Geopolitical political structure of Northeast, Mongolian, Xinjiang, Tibet, Yunnan and Guangxi provinces form frontier inland of China were summarized in this paper. The relationship between distribution of the Dao-di herbs and geopolitical political structure in above-mentioned provinces were described. In a strict sense, humanistic attribute of Dao-di herbs belonged to medical culture of Han Nationality. Distribution range of Dao-di herbs was determined by sphere of influence of central plains dynasty. Development of Dao-di herbs in the frontier inland area was unbalanced. The relationship between distribution of Dao-di herbs and geopolitical political structure proofed that natural attribute and humanistic attribute were inseparable. Recognition of this relationship is helpful to understand and develop genuine medicinal materials in frontier provinces.