A widely used application of the atomic layer deposition (ALD) and chemical vapour deposition (CVD) methods is the preparation of permeation barrier layers against water vapour. Especially in the field of organic electronics, these films are highly demanded as such devices are very sensitive to moisture and oxygen. In this work, multilayers of aluminium oxide (AlO x ) and plasma polymer (PP) were coated on polyethylene naphthalate substrates by plasma-enhanced ALD and plasma-enhanced CVD at 80℃ in the same reactor, respectively. As precursor, trimethylaluminium was used together with oxygen radicals in order to prepare AlO x , and benzene served as precursor to deposit the PP. This hybrid structure allows the decoupling of defects between the single AlO x layers and extends the permeation path for water molecules towards the entire barrier film. Furthermore, the combination of two plasma techniques in a single reactor system enables short process times without vacuum breaks. Single aluminium oxide films by plasma-enhanced ALD were compared to thermally grown layers and showed a significantly better barrier performance. The water vapour transmission rate (WVTR) was determined by means of electrical calcium tests. For a multilayer with 3.5 dyads of 25-nm AlO x and 125-nm PP, a WVTR of 1.2 × 10 −3 gm−2d−1 at 60℃ and 90% relative humidity could be observed.