Background: Plant essential oils are extensively utilized for their antimicrobial properties; however, the specific antifungal mechanisms of certain compounds are not well characterized. Geraniol, a naturally occurring monoterpene alcohol approved for use in foods, demonstrates potential efficacy against spoilage fungi, yet detailed mechanistic insights are lacking. Methods: In this study, we determined the minimum inhibitory concentration (MIC) and minimum fungicidal concentration (MFC) of geraniol against P. polonicum. We assessed the underlying mechanisms by evaluating membrane integrity, intracellular leakage, reactive oxygen species (ROS), antioxidant enzymes (superoxide dismutase [SOD], peroxidase [POD], catalase [CAT]), malondialdehyde (MDA) levels, ATP content, and ATPase activity. Inoculated yam slices were exposed to geraniol vapor, and we monitored sensory, physicochemical, enzymatic, and microbial parameters. Results: Geraniol exhibited a minimum inhibitory concentration/minimum fungicidal concentration (MIC/MFC) of 0.3 mL/L. It disrupted cellular membranes, induced leakage, generated ROS, and caused lipid peroxidation, leading to elevated levels of malondialdehyde (MDA). Additionally, geraniol activated antioxidant enzymes and impaired energy metabolism. Fumigation with geraniol dose-dependently delayed the deterioration of yam, reduced weight loss, preserved texture and color, inhibited polyphenol oxidase (PPO) and POD activities, enhanced CAT and SOD activities, lowered MDA levels, and suppressed bacterial growth. Conclusions: Geraniol inhibits P. polonicum through multiple mechanisms, including membrane disruption, oxidative stress, and interference with energy metabolism, thereby effectively preserving the quality of fresh-cut yam and demonstrating potential as a natural preservative.