Offset printed paperboard coated with polycaprolactone (PCL) polymer and nanoparticles was studied to elucidate the interactions and adhesion in two-layered packaging material. SiO2, Al2O3 and ZnO nanoparticles were used due to their specific interactions with water vapour that results in inhibition of water permeability. The good dispersion of nanoparticles in PCL matrix is crucial for enhancement of the barrier properties of coated paperboard. To gain an insight into the interactions between the nanoparticles, paperboard and PCL matrix determination of surface parameters was performed. The samples were characterized for water vapour permeability, mechanical and thermal properties. Their morphology was analysed by SEM microscopy, FTIR and UV/Vis spectroscopy. UV stability of the PCL nanocomposites coatings was also studied. It can be concluded that the nanoparticles have a significant effect on the surface properties and they influenced adhesion between paperboard and PCL coating.