Adopting ICP-AES and ICP-MS to determine the content of 53 elements (6 macro-elements, 47 trace elements), which used HNO₃ (5 mL) and H₂O₂ (2 mL) to digest Baishao (Paeoniae Radix Alba) by microwave. These herbs obtained from six producing areas in China, namely Xuanwu (Henan province), Shihezi (Xinjiang province), Zhongjiang (Sichuan province), Panan (Zhejiang province), Bozhou (Anhui province), and Heze (Shandong province). A certified reference material of Astragalus (GBW 10028, GSB-19) was used to assess the accuracy of the method. Except the slight change of Na and S in Xuanwu, the content of other producing areas followed the order of Ca > K > P > Mg > S > Na. The herbs of Shihezi (22,658 mg/kg) got the highest concentration of total elements, while the herbs of Panan (1.006 mg/kg) got the highest concentration of rare earth elements. The multi-element fingerprint map of Baishao was established, which was obviously different from other herbs. Meanwhile, the same method was adopted to determine the content of 50 elements in Baishao decoctions from three main producing areas. Compared with the herbs, each element was significantly reduced, and K was the highest concentration. The transfer rates of elements in Baishao decoctions followed the order (mean): As (55.79%) > Ni (55.19%) > Na (51.48%) > Mo (44.13%) > Ce (43.82%) > V (40.52%). The decoctions of Panan (0.122 mg/kg) got the highest content of rare earth elements. In all Baishao herbs and their corresponding decoctions, the levels of Cu, Cd, As, Pb, and Hg did not exceed the limits of the Green Trade Standards of Importing & Exporting Medicinal Plants & Preparations (WM2-2001) and Chinese Pharmacopoeia (2015).