Surfactants are always added to coating formulations to ensure good adhesion of edible coatings to a product’s surface and to maintain freshness. In this study, the effects of the mix surfactants Tween 20 and Span 80 with different hydrophile–lipophile balance (HLB) values on the film-forming ability, wettability, and preservation capacity of blueberry sodium alginate coating were investigated. The results indicated that Tween 20 obviously ensured favorable wettability and improved the uniformity and mechanical properties of the resulting film. While the addition of Span 80 reduced the mean particle size of the coating, enhanced the water resistance of the film, and helped to reduce blueberry weight loss. A sodium alginate coating with low viscosity and medium HLB could better inhibit the galactose, sucrose, and linoleic acid metabolism of blueberries, reduce the consumption of phenols, promote the accumulation of flavonoids, and thus display superior coating performance. In summary, sodium alginate coating with medium HLB had comprehensive advantages in film-forming ability and wettability and was conducive to the fresh-keeping role.