Based on clinical data of TCM formula for treating angina blood stasis syndrome, a Chinese herbal network for treatment of angina blood stasis syndrome was built up by using scale-free network, degree centrality, betweenness centrality and closeness centrality of Chinese herbs were calculated, and subgroup analysis was performed by using CONCOR method. It was found that salvia miltiorrhiza, rhizoma ligustici wallichii, astragalus root, safflower and radix Notoginseng exhibit high centrality, indicating they were crucial component of the formula to treat of angina blood stasis syndrome. Twenty seven subgroups were discovered, four subgroups are valuable for new TCM formula design. In order to analyze potential compatibility of Chinese herbs, CONCOR analysis was performed on subgroups to obtain network density, and provided explanations from Chinese medicine theory. Conclusion: Scale-free network calculation is a useful method to design TCM formula for treating angina blood stasis syndrome.