The invention discloses a method for synthesizing chloro-2, 2-di (perfluoroalkyl)-1, 3-dioxolane. The method comprises the following steps: mixing 2, 2-di (perfluoroalkyl)-1, 3-dioxolane liquid with acatalyst, introducing chlorine gas, heating to the temperature of 100-200 DEG C, and carrying out chlorination reaction to obtain 4, 4, 5, 5-tetrachloro-2, 2-di (perfluoro substituent)-1, 3-dioxolane. The perfluoroalkyl is independently selected from C1-4 perfluoroalkyls or fluorine atoms. According to the method, liquid-phase chlorination reaction is adopted, the reaction temperature is effectively reduced, the activity of the catalyst in the reaction is high, the side reaction is relieved, the requirements on equipment are reduced, the method is safe and simple to operate, the quality stability of the obtained product is high, and the industrial application feasibility is high.