The water vapor permeability of fat barrier films has been associated with structural characteristics such as polymorphism, crystal size, and chemical composition, among others. However, no mechanistic models have been proposed to describe this relationship. In this study, we have determined the effects of processing conditions on the structure and physicochemical characteristics of four fats and their relationship to water vapor permeability. Results suggest that the solids' volume fraction and the domain size of the fat crystals seem to be the most important factors controlling water vapor migration. Moreover, materials with relatively large crystalline domains will yield malleable films with relatively low storage and loss moduli and strain/stress at the limit of linearity high tan δ values. The structural effects on the permeability of fat films are related to the nanoscale of the material.