The work aims to develop a headspace gas chromatography-mass spectrometry (HS-GC-MS) method for the determination of hexamethyldisiloxane (D3), octamethyltrisiloxane (D4), decamethyltetrasiloxane (D5), and dodecamethylpentasiloxane (D6) in cigarette paper. The samples were equilibrated at 90 °C for 30 min in the headspace. Tetramethylsilane tetraethoxysilicate was used as the internal standard. The four kinds of methylcyclosiloxane in the trademark paper, inner liner paper and tipping paper were detected by selected ion monitoring (SIM) mode and quantified by the internal standard method. The detection limit was 0.000 2-0.002 9 mg/m2, the recovery rate was 87.0%-104.2%, and the precision was 0.3%-7.7%. Under the three-phase equilibrium state of headspace, the content of methylcyclosiloxanes in the gas phase was proportional to the content of the component in the original cigarette paper or standard solution. The overall content level of methylcyclosiloxanes in typical samples was in the order of trademark paper>inner liner paper>tipping paper, and the detected values were all less than the reference limit of 0.1% (mass fraction) in the EU. A stable and highly sensitive detection method for methylcyclosiloxanes in cigarette paper is established in this study, and the principle of three-phase equilibrium is analyzed, providing technical support for further improving the quality and safety evaluation methods of cigarette paper.