4-Amino-N-hexadecylbenzamide-graphene sheets (AHB-GSs), used in the preparation of the polyimide (PI) nanocomposite films, were synthesized by mixing a dispersion of graphite oxide with a solution of the ammonium salt of AHB. The atomic force microscope image of functionalized-GS on mica and a profile plot revealed the average thickness of AHB-GS to be ~3.21 nm. PI films were synthesized by reacting 4,4'-biphthalic anhydride and bis(4-aminophenyl) sulfide. PI nanocomposite films containing various contents of AHB-GS over the range of 0-10 wt% were synthesized using the solution intercalation method. The PI nanocomposite films under different thermal imidization temperatures, 250 and 350 oC, were examined. The graphenes, for the most part, were well dispersed in the polymer matrix despite some agglomeration. However, micrometer-scale particles were not detected. The average thickness of the particles was <10 nm, as revealed from the transmission electron microscope images. Only a small amount of AHB-GS was required to improve the gas barrier, and electrical conductivity. In contrast, the glass transition and initial decomposition temperatures of the PI hybrid films continued to decrease with increasing content of AHB-GS up to 10 wt%. In general, the properties of the PI hybrid films heat treated at 350 oC were better than those of films heat treated at 250 oC.