Yudanshen, the genuine medicinal materials of Danshen (Salvia miltiorrhiza), is a well-known traditional Chinese medicine (TCM) used to treat cardiovascular and cerebrovascular diseases. Although its pharmacological and antioxidative activities have been well-documented, there is little research on the hydroxyl radical (•OH) scavenging capacity of Yudanshen. In this study, we established multiple on-line high-performance liquid chromatography- chemiluminescence detector-diode-quadrupole-time of flight mass spectrometry (HPLC-CL-DAD-Q-TOF/MS) methods to rapidly screen and identify the •OH scavengers in Yudanshen simultaneously. The chromatographic and potency fingerprints revealed seventeen peaks that showed the inhibition of •OH. Fourteen of them were identified as danshensu, protocatechuic aldehyde, caffeic acid, ferulic acid, salvianolic acid F, salvianolic acid H/L, salvianolic acid G, salvianolic acid D, salvianolic acid E, rosmarinic acid, salvianolic acid B, isosalvianolic acid B, salvianolic acid A, and salvianolic acid C. This study explores the •OH scavenging activities of Yudanshen, and provides novel and powerful multiple on-line methods in the field of TCM for rapid screening and identification of •OH scavengers.