Four liquid solvents – 1,1,1‐trichloroethane, toluene, chlorobenzene and octane – are used as model contaminants in sorption experiments in polyethylene in order to study their diffusion behavior between 40 and 70 °C and assess the plausibility of utilizing recycled plastics as safe functional barriers in food packaging applications. A hybrid model that combines molecular and free volume theory elements is used to interpret the collected experimental data. This helps in evaluating microstructural characteristics pertaining to the penetrant‐polymer systems tested, correlating these characteristics with the molecular properties of the solvent, and has an eventual role in predicting sorption and diffusivity in similar untested systems.magnified image