A poly(amic acid) was prepared through the reaction of 4,4 '-(hexafluoroisopropylidene)diphthalic anhydride and 2,2 '-bis(trifluoromethyl) benzidine in N,N-dimethylacetamide. Hybrid films were obtained from blend solutions of the precursor polymer and the organoclay dodecyltriphenylphosphonium-mica, with the organoclay content varying from 0 to 1.0 wt %. The cast films of poly(amic acid) were heat-treated at different temperatures to create polyimide (PI) hybrid films. These PI hybrid films showed excellent optical transparency and were almost colorless. The intercalation of PI chains in the organoclay was examined with wide-angle X-ray diffraction and electron microscopy. In addition, the thermomechanical properties were tested with differential scanning calorimetry and thermogravimetric analysis, and the gas permeability was determined. The addition of only a small amount of the organoclay was sufficient to improve the thermal and mechanical properties of the PI, with the maximum enhancement being observed with 0.5 wt % organoclay. However, the water vapor permeability decreased with the clay loading increasing from 0 to 0.5 wt %. (C) 2007 Wiley Periodicals, Inc. J Appl Polym Sci 106: 4192-4201, 2007