The optical properties of food packaging frequently influence product appearance and consumer preference. As a novel food packaging strategy, starch-based coating, has demonstrated the ability to maintain quality and extend the shelf life of food, but its transparency has not been upgraded. The light-induced food oxidation caused by the enhancement of coating transparency also requires to be addressed. Herein, based on the screening results of five common commercial starches, phosphorylation and oxidation treatments were simultaneously administered on cassava starch to increase phosphorus content (0.287%) and reduce molecular weight (0.78 × 106 g/mol) and relative crystallinity (12.79%), resulting in a highly transparent dual modified starch-based coating. Ferulic acid was introduced to reduce UV transmission. The physicochemical properties of dual modified starch and its coating were comprehensively investigated using various methods. Compared with native starch-based coating, the as-obtained coating possessed relatively higher anti-wettability, mechanical strength, and thermal stability. More importantly, it exhibited high visible-light (87.06% at 600 nm wavelength) and extremely low UV transmittance (only 7.70% at 280 nm wavelength). The high transparency and photo-oxidation mitigation of the coating were also confirmed in actual fruits (e.g., strawberry and fresh-cut apples). This work provides a novel highly transparent coating that can preserve quality when used as a food packaging material.