Atomic layer deposition (ALD) has been widely reported as a novel method for thin film encapsulation (TFE) of organic light-emitting diodes and organic photovoltaic cells. Both organic and inorganic thin films can be deposited by ALD with a variety of precursors. In this work, the performances of Al2O3 thin films and Al2O3/alucone hybrid films have been investigated. The samples with a 50 nm Al2O3 inorganic layer deposited by ALD at a low temperature of 80°C showed higher surface roughness (0.503 ± 0.011 nm), higher water vapor transmission rate (WVTR) values (3.77 × 10−4 g/m2/day), and lower transmittance values (61%) when compared with the Al2O3 (inorganic)/alucone (organic) hybrid structure under same conditions. Furthermore, a bending test upon single Al2O3 layers showed an increased WVTR of 1.59 × 10−3 g/m2/day. However, the film with a 4 nm alucone organic layer inserted into the center displayed improved surface roughness, barrier performance, and transmittance. After the bending test, the hybrid film with 4 nm equally distributed alucone maintained better surface roughness (0.339 ± 0.014 nm) and barrier properties (9.94 × 10−5 g/m2/day). This interesting phenomenon reveals that multilayer thin films consisting of inorganic layers and decentralized alucone organic components have the potential to be useful in TFE applications on flexible optical electronics.