Provided are a protocatechuic acid and pulullan compounded chili coating film preservative and a usage method thereof. The preservative contains protocatechuic acid and pullulan, wherein the protocatechuic acid concentration is 121-125mg / L, and the pulullan concentration is 0.43-0.47%; Chilis are picked and then are soaked in the preservative for 1.3-1.7 minutes, the chilis are charged into a freshness retaining bag after natural air-drying, the bag is stored in an opened mode under the conditions of 20 DEG C and the humidity of 85%, the weight loss ratio, rotting rate and respiration intensity of fresh chilis can be remarkably reduced, degradation of chlorophyll, Vc, soluble protein and soluble solids is inhibited, the pericarp brightness, color, luster and color saturation can be effectively maintained, and the nutrition quality is kept. MDA accumulation is decreased, the membrane lipid peroxidation degree is reduced, the CAT activity is improved, and radical scavenging power is strengthened. The activity of POD, PPO and PAL and the increase of total phenol content can be effectively inhibited, the browning degree of the chilis is reduced, and the chili storage effect can be remarkably improved.