The influence of structure on the water vapor permeability (WVP) of fat films was determined in this study. Statistically significant (P < 0.1) correlations were found between WVP and chemical composition (% stearic acid), the Avrami index (n), the half-time of crystallization (t1/2), the maximum solid fat content, and crystalline domain size determined by powder X-ray diffraction (XS). Larger domain sizes translate into a smaller grain boundary surface area through which water vapor can migrate, resulting in a lower WVP. High values of XS were associated with fats with high SFC and stearic acid contents. These fats also crystallize rapidly, with low n and t1/2 values.