A series of poly(ether-block-amide) (PEBAX)/polyethylene glycol (PEG) composite films (PBXPG) were prepared by solution casting technique. This study demonstrates how the incorporation of different molecular weight PEG into PEBAX can improve the as-prepared composite film performance in gas permeability as a function of temperature. Additionally, we investigated the effect of PEG with different molecular weights on gas transport properties, morphologies, thermal properties, and water sorption. The thermal stability of the composite films increased with increasing molecular weight of PEG, whereas the water sorption and total surface energy decreased. As the temperature increased from 10 to 80 • C, the low (L)-PBXPG and medium (M)-PBXPG films showed a trend similar to the pure PEBAX film. However, the high (H)-PBXPG film with relatively high molecular weight exhibited a distinct permeation jump in the phase change region of H-PEG, which is related to the temperature dependent changes in the morphology structure such as crystallinity and the chemical affinity between the polymer film and gas molecule. Based on these results, it can be expected that H-PBXPG composite films can be used as self-ventilating materials in microwave cooking.