A series of linear aromatic copolyimides (Co-PIs) were synthesized by reacting 4,4′-biphthalic anhydride (BPA) with various molar contents of 2,2′-bis(trifluoromethyl)benzidine (TFB) and p-xylylenediamine (p-XDA) in N,N′-dimethylacetamide (DMAc). Co-PI films were fabricated by solution casting and thermal imidization with poly(amic acid) (PAA) on glass plates. The thermo-optical properties and gas permeabilities of Co-PI films composed of various molar ratios of p-XDA (0.2–1.0 relative to BPA) were investigated. Thermal properties were observed to deteriorate with increasing p-XDA concentration. However, oxygen-transmission rates (O2TRs) and optical transparencies improved with increasing p-XDA concentration. Co-PI hybrids with a 1:0.2:0.8 molar ratio of BPA:TFB:p-XDA and organically modified hectorite (STN) were prepared by the in situ intercalation method. The morphologies and the thermo-optical and gas permeation properties of the hybrids were examined as functions of STN loading (5–50 wt %). XRD and TEM revealed substantial increases in clay particle agglomeration in the Co-PI hybrid films as the clay loading was increased from 5 to 50 wt %. The coefficient of thermal expansion (CTE) and the O2TR of a Co-PI hybrid film were observed to improve with increasing STN concentration; however, its optical transparency decreased gradually with increasing STN concentration.