To improve the performance of edible coated films for the preservation of Shen Hong grapes, different concentrations of sucrose esters were added, and pullulan-collagen-sucrose ester composite films were prepared via the casting method. Through multidimensional characterization techniques, including scanning electron microscopy and thermogravimetric analysis, the effects of different sucrose esters on the micromorphology, molecular conformation, rheological properties, thermal stability, and barrier properties of the films were studied, and their preservation effects on grapes were evaluated. The results showed that sucrose esters had good compatibility with the pullulan-collagen matrix and exhibited synergistic effects with the polysaccharide and collagen molecules. The film-forming solution was a non-Newtonian fluid with good spreadability. Compared with pullulan-collagen films, the addition of sucrose esters increased the maximum disintegration temperature of the composite films from 310℃ to 332℃ , decreased light transmittance from 42% to 16.21%, and increased oxygen permeability from 2.38×10-4 g•(m2•s)-1 to 5.62×10-4 g•(m2•s)-1. In grape preservation by film coating, the optimal preservation effect was attained when the amount of sucrose ester was 1%, with a decay rate, weight loss rate, titratable acid content, and total bacterial count of 25.83%, 12.83%, 2.79%, and 5.32 log CFU/g, respectively. The shelf life of grapes was prolonged by 6 d compared with that of the uncoated group. In summary, the addition of sucrose ester helps improve the applicability of pullulan-collagen films as edible films.