This paper reported the permeability of four different organic compounds in low‐density polyethylene (LDPE), ethylene vinyl alcohol (EVOH), and in a multilayer film composed of them through the isostatic flow permeation measurement system. The methodology assumed that the nitrogen feed stream is saturated with organic vapour, and a chromatographic technique was used as a detector for the quantification of the permeate. The results were in general good agreement with literature reports, providing accuracy and reliability of measurement procedures. The permeability of LDPE increased with increasing hydrophobicity of organic compounds, but hydrophilic EVOH suggesting that there had been an effect of functional groups on permeability behaviour. The multilayer films were observed larger than expected because of the interface responsible for adhesive bonding of tie resins to EVOH by chemical interactions. Nonetheless, as an application of such multilayer structures, we suggested the method studied as feasible and possible tools for characterizing permeation properties against organic vapours.