Ultra-high molecular weight polyethylene (UHMWPE)/fuctionalized-MWNT hybrid films were prepared by the solution intercalation method, using 4-cumylphenol-MWNT (CP-MWNT) as the functionalized-MWNT. The variation of the thermomechanical properties, morphology, gas permeability. and optical transparency of the hybrid films with CP-MWNT content in the range of 0 similar to 2.00 wt% were examined. The newly synthesized UHMWPE/functionalized-MWNT hybrid films were characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and a universal tensile machine (UTM). It was found that the addition of only a small amount of functionalized-MWNT was sufficient to improve the thermomechanical properties of the UHMWPE hybrid films, with maximum enhancement being observed in the CP-MWNT loading in the range 0.50 to 1.00 wt%. The maximum enhancement in the oxygen gas barrier was also found at the functionalized MWNT content of 1.00 wt%. In this work, the thermomechanical properties and gas permeability of the hybrid films were found to be better than those of pure UHMWPE.