In this work, some multilayer coatings (two-layer, four-layer or six-layer) based on pullulan and chitosan for protecting papayas were prepared by the layer-by-layer technique. The papayas were coated by immersion and stored at 25 °C, 50% relative humidity or up to 14 days. Uncoated and monolayer-coated papayas were used as controls. The pullulan/chitosan coatings decreased the papaya weight loss, softening, color change (b*, ΔE), and pH, retarded the fall of titratable acidity and vitamin C, and maintained respiratory rate and soluble solid contents. Sensory quality evaluation demonstrated that pullulan/chitosan coatings effectively preserved papaya flavor and overall acceptance. In general, the four-layer coatings provided the best fruit preservation. In conclusion, multilayer pullulan/chitosan coatings are efficient in maintaining the post-harvest quality and prolonging the shelf life of fresh papaya.