Arsenic is one of the metals found in cured tobacco and mainstream cigarette smoke. Levels of arsenic in modern filtered cigarette smoke range from sub-ppm to a few tens of ppms. To enable accurate smoke toxicity assessment on arsenic in cigarette smoke, it is desirable to establish its chemical forms in addition to total quantities because different arsenic compounds possess different toxicological potentials.Progress has been made on measuring the arsenic speciation in tobacco and mainstream cigarette smoke by using a combination of synchrotron-based X-ray absorption spectroscopy and high-performance liquid chromatography- inductively coupled plasma mass spectrometry (HPLC-ICP-MS). In this paper, we describe the experimental procedures developed together with the main findings. A transient redox transformation between As(V) and As(III) was confirmed in freshly generated mainstream smoke. Potential areas for future research are highlighted in order to further our understanding of the speciation mechanism for arsenic in tobacco products.