Oligothiols are useful as building blocks in the construction of disulfide-based macrocycles and polymers or as ligands for coordination polymers. Above all, benzenehexathiol (BHT) is a particularly important molecule, as it is used to construct conductive two-dimensional MOFs. Despite the desire to clarify its structure and isolate it to high purity, the chemical instability of BHT has hampered single-crystal X-ray structure analysis of intact BHT. In addition, the synthesis of discrete disulfide molecules of BHT has not been reported. Here, we succeed in obtaining the single crystals of intact BHT, which is analyzed by single crystal X-ray structure analysis. Furthermore, the structures of a group of molecules with intermolecular disulfide bonds (BHT·4im and BHT2·2TBA, im = imidazole, TBA = tetrabutylammonium cation) obtained by processing BHT in the presence of bases are determined.