This paper presents the synthesis and characterization of polyimides containing a chiral (R, R) or (S,S) 1,3-bis(p - N,N'-dimetylaminobenzyl)-perhydrobenzimidazol-2-thion unit in the backbone. The reactions occur betweem equimolar amounts of a dianhydride and all aromatic dimethylamine. in the presence of the solvent N-methyl-2-pyrollidone (NMP). In this work, the chiral monomer RR and SS -1,3-bis(p - N,N'-dimethylaminobenzyl)-perhydrobenzimidazol-2-thion were used as diamines. The polyimides obtained were characterized bu thermogravimetry (TGA), differential thermal analysis (DTA), differential scanning calorimeter (DSC), infrared spectroscopy (FT-IR) and gel permeation chromatography (GPC). It was found that the composition of the polymer had a significant effect upon the thermal behavior of the material.