Postharvest diseases and quality degradation are the major factors causing food losses in the fresh produce supply chain. Hence, detecting diseases and quality deterioration at the asymptomatic stage of produce enables growers to treat the diseases earlier, maintain quality and reduce postharvest food losses. With the emergence of numerous technologies to detect diseases early and monitor the quality of fresh produce, such as polymerase chain reaction, gas chromatography-mass spectrophotometry, and near-infrared spectroscopy, electronic nose (EN) has also gained acknowledgement and popularity in the past decade as a robust and non-invasive analysis tool to detect odor profile and establish volatile biomarkers for metabolomics databases. However, literature reviewing the EN research on the early detection of diseases in produce after harvest is scarce. The fundamental concept of EN working principles (odor sampling, gas detection, and data acquisition method), as well as the application of EN as a whole, are covered in the first section of the review. An in-depth discussion of the application of EN analysis in the early identification of postharvest diseases and quality monitoring is provided in the subsequent sections, which is the key objective of this comprehensive review. The prospect, limitations, and likely future developments of EN in the postharvest sector are further highlighted in the last section.