Food packaging plays a crucial role in product storage, transportation and distribution. This study is dedicated to the development of high barrier blends for food packaging through the melt blending of polyethylene terephthalate (PET) and polyethylene 2,6‐naphthalate (PEN). The blends underwent comprehensive characterization involving chromaticity analysis, DSC, FTIR and XRD. Results indicated that the blend comprising 30 wt% PEN and 70 wt% PET exhibited superior structural properties, making it suitable for the production of beverage packing bottles. To evaluate the bottle properties, SEM, AFM, TG analysis and permeability testing were conducted. Comparatively, the barriers to O2, CO2, and water vapour of PEN/PET bottles were 3.52‐fold, 7.36‐fold and 2.25‐fold higher than PET bottles, and the mechanical properties and UV blocking properties have also improved. The PEN/PET bottles exhibited good thermal stability, with thermal shrinkage temperature and initial decomposition temperature at 87.5°C and 254°C, significantly higher than PET bottles (p < 0.05). Interestingly, the thermal shrinkage rate of PEN/PET bottles was measured at 87.5%, notably lower than that of PET bottles at 90.9%, indicating that PEN/PET bottles had good thermal stability. Additionally, beverage stored in PEN/PET bottles demonstrated lower dissolved oxygen content, suggesting promising applications for PEN/PET bottles in beverage packaging.