The pharmacodynamic material basis constitutes the central element of traditional Chinese medicine (TCM) in disease treatment. By summarizing the active compounds' characteristics, bioavailability, pharmacological effects, and molecular mechanisms, we can explain the complex interactions between TCMs and diseases. Previous studies have demonstrated that monoterpene glycosides and tannins are related to the pharmacological activity of Radix Paeoniae Alba (RPA). However, research on RPA has primarily focused on monoterpene glycosides, and the functional role of tannins in RPA has received little attention. Observations from animal studies indicate that monoterpene glycosides and tannins exhibit poor bioavailability. Carboxylesterase, produced by gut microbiota, is crucial for metabolizing these compounds in the intestine. Monoterpene glycosides and their gut metabolites can be absorbed into the bloodstream, exerting various pharmacological effects, including anti-inflammatory, immunomodulatory, and neuromodulator activities. In contrast, tannins consist of highly hydrophobic polyphenols that form insoluble protein-tannin complexes. Due to their inability to cross the intestinal barrier, tannins primarily exert localized pharmacological effects within the digestive system. This study systematically reviews the pharmacological activities and mechanisms of monoterpene glycosides and tannins in RPA, while establishing their therapeutic contributions to the herb's pharmacological effects.