Rice quality deterioration will cause grievous waste of stored grain and various food safety problems. Gas detection of volatile organic compounds (VOCs) produced by deterioration is a nondestructive detection method to judge rice quality and alleviate rice spoilage. This review discussed the research advance of VOCs detection in terms of nondestructive detection methods of rice quality deterioration, applications of VOCs in grain detection, inspection of characteristic gas produced during rice spoilage, rice deterioration prevention and control, and detection of VOCs released by rice mildew and insect attack. According to the main causes of rice quality deterioration and major sources of VOCs with off-odor generated during rice storage, deterioration can be divided into mold and insect infection. The results of literature manifested that researches mainly focused on the infection of Aspergillus in the mildew process and the attack of certain pests in recent years, thus the research scope was limited. In this paper, the gas detection methods combined with the chemometrics to qualitatively analyze the VOCs, as well as the correlation with the number of colonies and insects were further studied based on the common dominant strains during rice mildew, that is, Aspergillus and Penicillium fungi, and the common pests during storage, that is, Sitophilus oryzae and Rhyzopertha dominica. Furthermore, this paper pointed out that the quantitative determination of characteristic VOCs, the numeration relationship between VOCs and the degree of mildew and insect infestation, the further expansion of detection range, and the application of degraded rice should be the spotlight of future research.