As consumer awareness regarding health and nutrition continues to increase, there is a growing demand for fresh, nutritious fruits such as green grapes. However, the short storage life and susceptibility of these fruits to spoilage lead to significant commercial losses. Currently, the plastic wrap method is commonly used to keep green grapes fresh, but this packaging effect is limited and not environmentally friendly. Therefore, there is an urgent need to explore sustainable and effective preservation methods. In this study, a high-pressure microfluidization technique was employed to prepare an essential oil nanoemulsion with a ratio of Tween 80 to clove essential oil of 1:1, and a biopolymer-based film solution was prepared using dual-modified tapioca starch and chitosan loaded with clove essential oil nanoemulsion. The dual-modified tapioca starch/chitosan/SiO2/1.25 wt % clove essential oil (DM/Ceo-1.25) solution coating was successfully applied for the packaging and preservation of fresh green grapes. Compared with the CK and polyethylene wrap (PE) groups, the DM/Ceo-1.25 coating significantly improved the quality of the green grapes, increasing the storage period of the green grapes from 4 to 8 days at room temperature. On the 10th day of storage, the coated grapes retained significantly better quality, with a hardness of 4.01 N, a titratable acidity of 1.625%, an anthocyanin content of 1.013 mg/kg, and a polyphenol content of 21.32 μg/mL. These results indicate that the DM/Ceo-1.25 solution coating developed in this study can be used as a new active material for fruit preservation and provides ideas for the development of safer and more sustainable food packaging.