A study was conducted that demonstrated that the blending of edible oils leads to changes in surface tension, thermal properties, viscosity, and oil penetration times through a barrier-coated paperboard. The results emphasize the significance of testing the oil and grease resistance (OGR) oil blends in order-to verify the suitability of the packaging material for real-life end-use applications. The results of the OGR determinations suggest that hydroxypropylated-starch-based composite coatings containing an oleophilic high aspect ratio mineral can be tailored for food shaving different fatty acid compositions by varying the pigmentation level. Compared to standard OGR tests, confocal laser scanning microscopy (CLSM)-based techniques make it possible to evaluate the oil penetration time and its diffusion behavior very accurately, both inside the coating layer and in the bulk matrix. It was found that, at room temperature, coconut oil tends to crystallize inside the substrate, inducing swelling of the coating layer, which probably has an influence on the physicomechanical properties of the packaging material.