In this study, we report a rational approach to design a novel VOC-free self-stratifying light-curable coating containing bio-renewable materials based on the methacrylated gelatin (GelMA) and acrylated epoxidized soybean oil diluted by the acrylated glycidyl neodecanoate (AESO-CE). The self-stratified structures of the AESO-CE/GelMA coatings attained through the visible light curing were recognized by SEM-EDX and water contact angle (WCA) analyses. Hildebrand (δHild) and Hansen solubility parameters (δHans) of AESO-CE and GelMA were calculated by molecular dynamics simulation and Hansen solubility spheres, respectively. It was revealed that the computational immiscibility results had an illustrative agreement with the experimental incompatibility observations in different AESO-CE/GelMA weight ratios over time. Furthermore, the findings demonstrated that surface tension and solubility parameters can be considered when dealing with self-stratification prediction in the gelatin-soybean oil-based coatings. The results indicated that the coatings with both hydrophobic-hydrophilic natures with WCA of 66–84° can be achieved by a fast curing reaction without the aid of solvent evaporation. Besides, it was concluded that the stratifying level and surface hydrophobicity properties have been significantly affected by the AESO-CE/GelMA weight ratio and the mixture viscosity. Accordingly, this investigation provides a helpful insight to develop a green coating exhibiting gradient hydrophobic behavior, as a promising candidate for advanced breathable food and bio-applications.