Wearing masks has been generally recommended to reduce the spreading of COVID-19. However, little is known about its effects on metabolic VOC changes in human body. To explore how the duration of wearing masks influences VOC metabolism in the human body, the essay used a self-developed electronic nose to analyse exhaled breath samples from 10 healthy individuals in this study. Firstly, polytetrafluoroethylene sampling bags are used to collect breath samples after volunteers wearing masks for 1h, 2h, 3h, 4h, and 5h. Secondly, data pre-processing, including baseline calibration and normalization are carried out. Thirdly, the study used LDA for dimensionality reduction on the original data to extract 4 features. Fourthly, differences in the length of time of wearing masks are analysed. Then, 4 algorithms were applied for cluster analysis based on extracted features. Moreover, 3 supervised classification algorithms were used to recognize the duration of wearing masks. Finally, multi-dimensional linear regression is used to study the possibility of predicting the duration of wearing masks based on breath signals acquired through electronic noses. As a result, the first feature extracted by LDA significantly differs from each other in the duration of wearing masks (p<0.05). Cluster analysis results show that the optimal internal parameters Adjusted Rand Index, Adjusted Mutual Information, Homogeneity and V-measure reach 80.2%, 81.5%, 83.5% and 83.7% respectively. Using 5-fold cross-validation on the K nearest neighbour classification model, the best accuracy of recognizing durations of wearing a mask reaches 88%. R-square of multi-dimensional linear regression reaches 92.5%, which shows excellent fitting performance. It can be concluded that the VOC metabolism of the human may change with the duration of wearing masks. Further, “breath prints” obtained by electronic nose may have the potential to predict the effective time and even the quality of masks.