This study investigates natural-based blends of glutinous rice starch (GRS) and chitosan (CS), varying their molar composition (0:100, 30:70, 50:50, 70:30, and 100:0) to explore their interaction dynamics. Our findings illustrate the versatility of these blends in solution and film forms, offering applications across diverse fields. Our objective is to understand their impact on coatings designed to extend the post-harvest shelf life of mangoes. Results reveal that increasing chitosan content in GRS/CS blends enhances mechanical strength, hydrophobicity, and resistance to Colletotrichum gloeosporioides infection, a common cause of mango anthracnose. These properties overcome limitations of GRS films. Advanced techniques, including FTIR analysis and stereo imaging, confirmed robust interaction between GRS/CS blend films and mango cuticles, improving coverage with higher chitosan content. This comprehensive coverage reduces mango dehydration and respiration, thereby preserving quality and extending shelf life. Coating with a GRS/CS blend containing at least 50% chitosan effectively prevents disease progression and maintains quality over a 10-day storage period, while uncoated mangoes fail to meet quality standards within 2 days. Moreover, increasing the starch proportion in GRS/CS blends enhances film density, optical properties, and reduces reliance on acidic solvents, thereby minimizing undesirable changes in product aroma and taste.