The invention relates to a method for simultaneously determining twelve alkaloids in a cigarette smoke particulate matter, and belongs to the technical field of physical and chemical analysis. The method comprises the following steps: 1, capturing the cigarette mainstream smoke particulate matter with a Cambridge filter by using a linear or rotating disc smoking machine; 2, dissociating alkaloids in the Cambridge filter by using a 5% aqueous sodium hydroxide solution; 3, carrying out liquid-liquid oscillation extraction by using a dichloromethane/methanol mixed solution as an extracant; and 4, standing the obtained solution at room temperature, taking the obtained lower organic phase, filtering the lower organic phase by a 0.22 [mu]m organic phase filter membrane, transferring the filtered lower organic phase to a chromatography bottle, and carrying out GC-MS analysis. The average standard addition recovery rate of the twelve tobacco alkaloids is 94-108%, the precision is not more than 6.8%, the detection limit of the method is 0.18-1.76 [mu]g/cigarette, and the method has the advantages of simplicity in operation, high flux, high sensitivity, good recovery rate and good repeatability.