Colorimetric starch film containing anthocyanins is extensively used in eco-friendly intelligent food packaging, but its high water wettability limits its practical application in the food industry. Herein, a super anti-wetting colorimetric starch film was prepared by surface modification with a nano-starch/poly-(dimethylsiloxane) (PDMS) composite coating. The water sensitivity, optical properties, mechanical properties, surface morphology, and surface chemical composition of this film were systemically investigated by multiple methods. The obtained film exhibited an extremely high water contact angle (152.46 degrees) and low sliding angle (8.15 degrees) owing to the hierarchical micro-/nanostructure formed by nano-starch aggregates combined with the low-surface-energy PDMS covering. The anti-wettability, optical barrier, and mechanical properties of this film were also significantly improved. The self-cleaning and liquid-food-repelling abilities of this film were comprehensively confirmed. Moreover, this super anti-wetting colorimetric starch film can be applied to monitor the freshness of aquatic products without being disabled by water.