Abstract Traditional Chinese medicine contains arsenic (As), which in the natural environment accumulates in plants during the growth of Chinese medicinal materials; there are mineral medicines containing As in Chinese patent medicine such as As4S4, As2S3, etc. Due to the toxicity of As-containing compounds and its role in inflammation and treatment of cancers such as leukemia, it is necessary to analyze the chemical form of As. A comprehensive investigation of the compound forms of heavy metals rather than the simple total amount of elements will lay the foundation for the scientific and objective evaluation of the safety of heavy metals. This article summarizes the speciation of As in bulk Chinese medicinal materials and Chinese patent medicines in recent years, and reviews the main research methods of As speciation analysis. The separation and detection combined analysis method focuses on the high-performance liquid chromatography-plasma mass spectrometry and high-performance liquid chromatography-hydride generation-atomic fluorescence spectroscopy, etc. Taking the advanced synchrotron radiation source as the research platform, the use of X-ray near edge absorption fine structure spectrum and micro-area X-ray fluorescence analysis as a microscopic analysis technique supports direct analysis of the As speciation in situ. It is the most promising morphological analysis method.