Thin-film encapsulation (TFE) with strong barrier properties is essential for dependable flexible display. Hybrid Al2O3 and polymer multi-layered structures are considered the most promising TFE technology. However, hydrolysis of Al2O3 becomes severe with increased temperature and humidity, threatening the reliability of TFE. In this work, Alucone is introduced in the Al2O3/NEA multi-layers, where the Alucone can serve as a hydrolysis inhibition layer, to improve its reliability. In addition, Al2O3 is permeated into the NEA polymer to further improve the barrier performance of Al2O3/NEA multi-layers. The results show that the insertion of Alucone can inhibit effectively the hydrolysis of Al2O3 in the accelerated test environment. The complete interfacial infiltration of Al2O3 into NEA polymer can further improve the barrier performance. The water vapor transmission rates of (Al2O3/Alucone)3/NEA (named AAN composite films) can reach 0.27 × 10−6 g/m2/day. The barrier performance of AAN composite films remains robust even after bending tests and stability examinations. The OLED encapsulated by the AAN composite films, only less than 10 % brightness decline occurs after 7 days, illustrating that AAN composite films can extend the lifetime of OLED. The results demonstrate that the AAN composite films is anticipated to hasten the commercialization of flexible displays.