Shengmaisan is a recipe of traditional Chinese medicine, which is composed of three herbs. The interaction among the components from the three herbs of Shengmaisan is investigated using FT-IR, Matrix Assistant Laser Desorption/Ionization Time of flight mass spectrometry (MALDI TOF MS) and TEM observation. Interactions among various components from different herbs cause enhancement of the solubility of some component and suppression of the solubility of others. Results from MALDI-TOF MS show that some components found in the decoction from a single herb disappear when different herbs are decocted together. On the other hand, new substances are produced when two and/or three herbs of Shengmaisan are decocted together. TEM showed that vacuoles formed in the decoction from two and/or three herbs of Shengmaisan but did not occur in any decoction from a single herb. This result provides us direct evidence that the solubilized structure is formed by the interaction among the components from different herbs. This knowledge helps us to understand the therapeutical effects of traditional Chinese medicine.