A previously developed model which effectively predicts the probability of olive oil reaching the end of its shelf-life within a certain time frame was tested for its response when the convective diffusion of oxygen through packaging material is taken in account. Darcy’s Law was used to correlate the packaging permeability with the oxygen flow through the packaging materials. Mass transport within the food-packaging system was considered transient and the relative one-dimensional differential equations along with appropriate initial and boundary conditions were numerically solved. When the Peclet (Pe) number was used to validate the significance of the oxygen transport mechanism through packaging, the model results confirmed the Arrhenius type dependency of diffusion, where the slope of the line per material actually indicated their –Ea/R. Furthermore, Pe could not be correlated to the hexanal produced in samples stored under light. Photo-oxidation has a significant role in the oxidative degradation of olive oil confirmed by the shelf-assessing test. The validity of our model for the oxygen diffusion driven systems, was also confirmed, for that reason the predictive boundaries were set. Results safely indicated the significance of applying a self-assessing process to confirm the packaging selection process for oxygen sensitive food via this model.