Self-stratification is an innovative one-step process used to design multi-functional coatings gathering simultaneously in a one-pot formulation the primer, the intermediate layer and the top coat properties. Many selfstratifying coatings contain oil-based epoxy resins but the literature is scarce in the development of “greener” solutions. In this work, silicone resins and bio-based epoxy resins were dissolved in various solvent blends, applied on a composite substrate and cured under different conditions to obtain stratified coatings. To reach aperfect stratification, the influence of various parameters including (i) the surface tension and the polarity of the resins, (ii) the solvents volatility, (iii) the curing temperature and (iv) the reactivity of the epoxy/amine reaction was studied by a systematic approach. In accordance with the literature, it was demonstrated that a large difference in surface energy and polarity favors resins separation. The volatility of the solvent blend was also shown to be a key factor in the stratification process. However, the predominant parameter, rarely taken into account, isthe curing temperature, which impacts the cross-linking reaction of the epoxy resin. The increase in molecular weight (MW) of epoxy resins due to the cross-linking reaction favors the incompatibility between resins by increasing the difference in MW between epoxy and silicone resins. Thus, optimization of process conditions allowed the design of perfectly stratified bio-based epoxy/silicone coatings. The mechanism of film stratification was also elucidated thanks to in-situ analyses.