In this study, lychee (Litchi chinensis Sonn.) pericarp powder was added to chitosan (CHS) matrix to develop active packaging films, and their structure, physicochemical, antibacterial, antioxidant, and functional properties were investigated. FT-IR results showed that intermolecular hydrogen bonds were formed between CHS and polyphenols in lychee pericarp powder (LPP), and the intermolecular interaction interfered with the assembly of CHS into semi-crystal structure, which reduced the crystallinity of CHS film. Incorporation of LPP significantly reduced water vapor permeability, water solubility, swelling degree, and elongation at break of CHS film (p < 0.05). However, UV-visible light barrier, tensile strength, and antibacterial and antioxidant properties of CHS films were increased by LPP incorporation. CHS-LPP film remarkably lowered the weight loss, firmness, titratable acidity, and total soluble solids of fresh-cut apple after five days storage. CHS-LPP film packaging effectively inhibited the browning of fresh-cut apple and the reduction of polyphenol content in apple juice caused by polyphenol oxidase (PPO)-mediated oxidation during storage. Therefore, CHS-LPP films have great potential as food packaging material to ensure the quality and extend the shelf life of food products.