Post-harvest management of agricultural products is crucial for minimizing spoilage and economic losses. Volatile organic compounds (VOCs) have emerged as effective indicators of early-stage deterioration, offering a promising approach to improving detection methods. This review examines the role of VOCs in spoilage identification, emphasizing key markers such as terpenes, ketones, esters, and aldehydes in fruits, vegetables, grains, and legumes. Various detection techniques-including spectrometry, electronic noses, spectroscopy, and sensor arrays-are evaluated and compared for their potential to assess spoilage and freshness by correlating their limits of detection (LOD) with typical VOC concentrations in agricultural scenarios. Future development trend in VOC research focus on enhancing sensor sensitivity, developing portable detection devices, integrating VOC monitoring with smart systems, and leveraging artificial intelligence for predictive analysis. These advancements aim to optimize post-harvest management strategies and improve food safety through more accurate and timely spoilage detection.