Plant extracts represent a rich repository of metabolites with antioxidant and antimicrobial properties. Neem (Azadirachta indica) is a medicinal plant considered the tree of the 21st century. In this study, we investigated the antioxidant and antimicrobial effects of propyl disulfide (PD), a major volatile compound in neem seed, against the pericarp browning (BI), microbial decay incidence (DI), and water loss of longan fruit. Fresh longan cv. Shixia samples were packaged in oriented polypropylene (OPP) and polyethene (PE) packages of different thicknesses (20, 40, and 60 µm). Sterile gauze was fixed inside the packages and 500 uL of PD was placed on them to avoid the direct contact of PD with fruit samples. Packages were sealed immediately to minimize vaporization and stored at 12 ± 1 °C for 18 days. Fruit samples packaged in open net packages served as controls. The results showed that fruit treated with PD in OPP and PE packages significantly prevented losses of water, DI, and BI compared to control treatment. PD also maintained the color, TSS values, TA values, pH values, high peel firmness, high TPC content, and high TFC content, and reduced the activity levels of PPO and POD. Scanning electron microscope (SEM) analysis indicated that the exocarp, mesocarp, and endocarp of longan peel were smooth, uniform, and compact with no free space compared to control, where crakes, a damaged and loose structure, and a lot of fungal mycelia were found. The shortest shelf life of 9 days was observed in control as compared to 18 days in OPP-20 and OPP-40; 15 days in OPP-60, PE-20, and PE-40; and 12 days in PE-60 packaging films. Therefore, PD as a natural antioxidant and antimicrobial agent, in combination with OPP-20 and OPP-40 polymeric films, could successfully be applied commercially to extend the postharvest shelf life of longan.