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The health and environmental concerns of the usage of non-biodegradable plastics have driven efforts to explore replacing them with renewable polymers. Although starch is a vital renewable polymer, poor water resistivity and thermo-mechanical properties have limited its applications. Recently, starch/synthetic biodegradable polymer blends have captured greater attention to replace inert plastic materials; the question of ‘immiscibility’ arises during the blend preparation due to the mixing of hydrophilic starch with hydrophobic polymers. The immiscibility issue between starch and synthetic polymers impacts the water absorption, thermo-mechanical properties, and chemical stability demanded by various engineering applications. Numerous studies have been carried out to eliminate the immiscibility issues of the different components in the polymer blends while enhancing the thermo-mechanical properties. Incorporating compatibilizers into the blend mixtures has significantly reduced the particle sizes of the dispersed phase while improving the interfacial adhesion between the starch and synthetic biodegradable polymer, leading to fine and homogeneous structures. Thus, Significant improvements in thermo-mechanical and barrier properties and water resistance can be observed in the compatibilized blends. This review provides an extensive discussion on the compatibilization processes of starch and petroleum-based polymer blends.