Effects of oligochitosan (OCH) on postharvest rot caused by Alternaria alternata in Chinese jujube (Zizyphus jujuba Mill. cv. Dongzao) fruit were investigated. An in vitro test indicated that mycelial growth of A. alternata was strongly suppressed by OCH at 0.5, 1, 2, 5, 10, 15, or 20 g/liter. The half-inhibition concentration of OCH against this fungus was 0.76 and 1.69 g/liter on days 4 and 6 of incubation, respectively. Lesion area and disease incidence in the jujube fruit inoculated with A. alternata were remarkably reduced by the OCH treatments at concentrations higher than 1 g/liter, but 5 g/liter OCH was considered the optimal treatment for inhibiting disease development. OCH also significantly reduced postharvest natural decay, promoted fruit firmness, delayed decline in soluble solids and loss of ascorbic acid, and increased total phenolic compounds during storage at 0°C and 85 to 95% relative humidity. Biochemical evaluations revealed that the activities of the main defense-related enzymes in the jujube fruit, including phenylalanine ammonia-lyase, peroxidase, chitinase, and β-1,3-glucanase, were significantly enhanced (P < 0.05) by OCH treatment. OCH increased superoxide dismutase activity but decreased catalase activity and, consequently, elevated hydrogen peroxide levels in the fruit. These results suggest that OCH might trigger several defense mechanisms in the jujube fruit for disease control in addition to its direct antifungal activity. OCH could be a viable alternative to conventional control of postharvest diseases of horticultural products.