The feasibility of corn zein nanocomposite (CZNC) coatings as an alternative to synthetic polymer barrier layer on polypropylene (PP) films was examined. The effect of layered silicate content in the CZNC layers on the barrier and surface hydrophobicity of the CZNC-PP films were investigated. Incorporation of organomodified montmorillonite (OMMT) by solution intercalation into zein matrix significantly improved oxygen and water vapor barrier of coated PP films. The barrier properties were also investigated theoretically by using various phenomenological permeability models. Tortuous permeation path formed by the fine delamination of nanoclays was found to be responsible for the barrier improvements in zein layers. In conclusion, durable CZNC-PP laminates were developed. CZNC coating of PP films has reduced the oxygen permeability nearly four times, while water vapor permeability reduced by 30% with 5wt.% OMMT content in 5.9μm corn zein coating.