In order to deal with the problems of the unstable transformation process and volatile palatability of coumarin compounds in C. chinensis, a method for the extraction, separation, and purification of coumarins in Chinese medicinal materials based on electrochemistry was prepared. First, an electrochemical distance-independent localization mechanism is used to determine node locations and routing mechanisms, and an extraction method is designed to achieve automatic and accurate real-time collection, aggregation, and transmission of ever-growing data. Environmental information for C. chinensis is collected. On the basis of this method, according to the chemical properties of coumarin and the extraction rate of coumarin as an index, the two-phase solvent extraction method and macroporous adsorption resin method were used to separate and purify it, and the best separation was determined. The purification process achieves efficient purification of coumarin. The experimental results show that the retention rate of coumarin by ethyl acetate is 34.5–56.8% higher than that of the other three extractants. When the optimal process determined in this study is adopted, the coumarin adsorption rate is greater than 98% and the recovery rate is greater than 85%. The purity of samples with 50% coumarin content can be increased to more than 97%, which verifies the correctness and advancement of the separation and purification process in this study.