The invention relates to a method for analyzing the speciation of arsenic elements in smoke of cigarettes. The method is characterized by comprising the steps of capturing arsenic in particulate matter of smoke by virtue of a rotary disc smoking machine with an electrostatic capturing device, extracting arsenic compounds of different speciation in the particulate matter by virtue of a diammonium hydrogen phosphate solution, and quantitatively analyzing the release amount of arsenic elements of different speciation by virtue of an HPLC-ICP-MS (High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry) technique so as to realize the quantitative analysis on the speciation of the arsenic elements in main stream smoke of the cigarettes. The method has the advantages that a sample pretreatment process is simple, convenient and rapid, the consumption amount of an extraction reagent is little, a separating effect of the speciation of As elements is good, the analytical interference is less, the sensitivity is high, the linearity range is wide, the precision is high, and a technical support is provided for accurately estimating the security risk of the As elements in the main stream smoke of the cigarettes.