Litchi (Litchi chinensisSonn.) fruit deterioration occurs rapidly after harvest and is characterized by pericarp browning, pulp softening, and decay. In this study, we found that calcium chloride (CaCl2) treatment (5 g L−1CaCl2solution vacuum infiltration for 5 min) affected the cell wall component contents and cell wall-degrading enzyme activities of litchi fruit during storage at room temperature. CaCl2treatment significantly increased the contents of Ca2+and cellulose, while it decreased the water-soluble pectin content, and the activities of polygalacturonase,β-galactosidase, and cellulase in the litchi pericarp. Meanwhile, the treatment resulted in significantly increased contents of Ca2+, water-soluble pectin, ionic-soluble pectin, covalent-soluble pectin and hemicellulose, and upregulated activities of pectinesterase andβ-galactosidase, while significantly decreasing the activities of polygalacturonase and cellulase in litchi pulp. The above results indicate that CaCl2treatment strengthened the cell wall structure of litchi fruit. More importantly, the enzymatic browning of the pericarp, softening of the pulp, and disease incidence were delayed. The treatment had a more pronounced effect on the pericarp than on the pulp. We consider CaCl2treatment to be a safe and effective treatment for maintaining the postharvest quality of litchi fruit.