Objective: A non-destructive testing technology combining powder X-ray diffraction (PXRD) and electron spin resonance (ESR) was established to make the quality control and identify the sources of trace elements of 10 commercially available scorpions. Methods: The characteristic marker peaks of Scorpion were obtained by PXRD spectrum simulation method to identify the content and source of NaCl. Some of the trace elements were analyzed by ESR technique. Results: (1) The NaCl content of 10 randomly purchased commercial scorpions was 4.35~13.33 g/100 g, the alum content was 3.73~11.27 g/100 g, the silicon content was 2.38~4.40 g/100 g. (2) The PXRD peaks in the scorpion originate from sodium chloride (NaCl) crystal and sodium sulfate (Na2SO4) crystal. The inorganic salt Na2SO4 originates from the scorpion itself, while NaCl is added through the concocting process. (3)There is a signal with g = 2.003 and a Mn2+ signal with six-line characteristics in the ESR spectrum. (4) In the ESR test, the dried scorpion after the dissolution experiment appears a weak broad signal of g = 4.3 and a signal of g = 2.17 which belongs to the signal of Fe3+and Cu2+, respectively. This phenomenon indicates that Fe3+ and Cu2+ ions are contained in the scorpion itself. (5) Atom emission test on the dissolution-experiment-acqueous solution confirmed that the Mn2+ in the scorpion originated from salt, rather than the scorpion itself. Conclusion: The combined application of PXRD and ESR technology can establish a non-destructive test technology, which can be used for the quality control of Scorpion and the source of transition metal elements.