The pericarp of the Longkong fruit rapidly browns during ambient storage, typically reducing its shelf life to between 3 and 7 days. Recently, n-butanol has demonstrated a promising effect in preventing this deterioration, extending the shelf life of tropical fruits to more than a week. The present study exploited this opportunity to examine the exogenous application of aqueous n-butanol at various concentrations (0.2–0.6%) in controlling pericarp browning and suppressing different oxidoreductase enzymes in the pericarp under prolonged ambient storage conditions (8 days). Every two days, the fruit pericarps were tested for color (lightness (L*), redness (a*), and yellowness (b*)), browning index (BI), membrane permeability loss (MPL), malondialdehyde (MDA) content, total phenolic content (TPC), and reactive oxygen species (ROS). Enzymes including phenylalanine ammonia lyase (PAL), polyphenol oxidase (PPO), phospholipase D (PLD), lipoxygenase (LOX), superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase (GPX) were also analyzed. All sample test results showed that increased storage significantly impacted color characteristics (decreased L*, b* and increased a*, and BI). MPL, MDA, and ROS also continuously increased. Furthermore, the browning-related enzymes (PAL and PPO), membrane-degrading enzymes (PLD and LOX), and antioxidant enzymes (SOD, CAT, and GPX) continuously increased in all pericarp samples throughout the storage. Among the samples, pericarp color, BI, MPL, MDA, PAL, PPO, PLD, and LOX were significantly high in the control samples, consequently adversely affecting the quality and shelf life of Longkong. On the other hand, the n-butanol-treated samples significantly controlled the loss and all problematic enzymes while improving the activities of SOD, CAT, and GPX in the pericarp. Furthermore, the positive effect of n-butanol application was dose-dependent; higher concentrations (0.4–0.6%) performed well in protecting the fruit from deterioration.