Four bromine-substituted 2,5-di(1,3-dithiol-2-ylidene)-1,3-dithiolane-4-thione derivatives, 1a, 1b, 1c, and 1d, were synthesized, and their physical properties were investigated. These compounds were obtained from the reaction of a corresponding zinc complex of 2-(1,3-dithiol-2-ylidene)-1,3-dithiole-4,5-bis(thiolate) derivatives and corresponding tetrafluoroborate salts of 1,3-dithiol-2-ylium derivatives. Recrystallization of la from carbon disulfide and n-hexane gave single crystals suitable for X-ray structure analysis. In the crystal, la molecules are one-dimensionally stacked and one molecule is rotated relative to the neighboring molecules by an angle of 92 degrees about its longer molecular axis. On the (010) plane, the molecules were arranged in a zigzag manner along the a axis. This interesting feature is accomplished by intermolecular S center dot center dot center dot Br halogen bonds.