To effectively obtain 1,1,9,9-tetrabromo-[2,2]-paracyclophane in a short time without using carbon tetrachloride as the solvent which is difficult to use in an industrial scale by carrying out the bromination of a specific paracyclophane with bromine in the presence of a radical initiator using tetrachloroethylene as the reaction solvent.

The objective compound of formula II is obtained by brominating the [2,2]-paracyclophane of formula I by bromine using preferably 15 to 20 times of tetrachloroethylene as the reaction solvent in the presence of the radical initiator (e.g.; benzoyl peroxide). The sequential addition of the radical initiator and the bromine is preferred. The preferred reaction temperature is 110°C to the refluxing temperature. The preferred amount of the bromine is 4.8 to 6.5 moles per 1 mole of the compound of formula I. After the reaction, hydrogen bromide and the bromine is removed by decompression under cooling or blowing nitrogen. Further cooling, filtering and washing affords the objective compound.