The invention belongs to the technical field of smoke analysis, and particularly relates to a method for extracting, separating and analyzing Cr (III) and Cr (VI) in the smoke of cigarettes. The method is characterized by mainly comprising the following steps of (1) trapping chromium in the smoke of the cigarettes; (2) treating gas phase matter and particle phase matter in the smoke; and (3) carrying out high performance liquid chromatography (HPLC)-inductively coupled plasma (ICP)-mass spectrometry (MS) online separation and analysis. The method has the advantages that after a rotary table smoke sucking machine-electrostatic trapping method is adopted, chromium with different element forms in the main stream smoke of the cigarettes can be trapped; Cr (III) and Cr (VI) in the smoke can be directly extracted by mobile phase; Cr (III) is enable to have a complexation reaction with ethylene diamine tetraacetic acid (EDTA) at certain temperature; after that, base line separation is carried out on Cr (III) and Cr (VI) by a chromatographic separation column, and 52Cr is measured by ICP-MS, so that the quantitative analysis of Cr (III) and Cr (VI) in the smoke of the cigarettes can be realized. After the method is adopted, the sample pretreatment is simple, convenient and rapid, and the quantitative analysis of Cr (III) and Cr (VI) can be completed within 10 minutes, so that a technical support is provided for accurate evaluation of the harm of heavy metal chromium in the smoke to a human body and the environment.