Grapes vaporize volatiles in specific compositions and concentrations during deterioration processes .Our previous study demonstrated that it is possible to analyze grapes spoilage stages by using the infrared spectra of their volatiles .However , only the spectral characteristics of alcohol ,ethyl acetate and carbon dioxide were observed in the experiment because of the low concentration of the volatiles .In this paper ,the sensitivity of the spectrometry system was enhanced by increasing the optical‐path with multi‐reflecting mirrors .We used the new spectrometry system to study the details of the infrared spectra of the vola ‐tiles from grapes during spoilage ,and observed the spectral characteristics of several kinds of ethanol ,esters ,aldehyde and eth‐ylene .The concentrations of some components in the volatiles changes with storage time ,which can be a biomarker to represent the spoilage stages of grapes .Chemometrics were used to analyze the spectral bands of ethanol and esters ,demonstrating there are obvious differences between fresh and decayed grapes .Furthermore ,we developed a simplified E‐nose system comprised by sensor array ,based on the results of spectral analysis .The classification and discrimination of grape spoilage were tested with E‐nose .This was a further study of the previous publication and had given a more precise observation of the infrared spectral characteristics of the volatiles from decayed grapes .This study provided a basis for developing real‐time monitoring techniques of fruits deterioration .%葡萄在劣变时会挥发出特定成分和浓度的气体。在变质葡萄的挥发物红外光谱中发现了乙醇、乙酸乙酯和二氧化碳的光谱特征。通过多次反射的光学系统提高了光谱测量的光程，从而获得了更高的探测灵敏度。利用新型光谱测量系统进一步研究了葡萄劣变过程中挥发物的精细化特征，并证实了其中含有多种醇类、酯类、醛类和乙烯的光谱特征。部分挥发物的浓度随贮藏时间展现规律性的变化，可以以其为生物标志物来表征葡萄的变质程度。进一步以光谱观测规律为基础研制了由传感器阵列组成的电子鼻，通过对特定挥发物的定量化测量实现葡萄变质的分类和预警。揭示了更为精细的葡萄劣变过程中挥发物的光谱特征变化规律，证实了通过挥发物测量鉴别水果变质的可行性，为开展水果变质的实时监测技术研究提供了理论和技术参考。
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