In response to one of the most important challenges of the century, i.e., the estimation of the food demands of a growing population, advanced technologies have been employed in agriculture. The potato has the main contribution to people’s diet worldwide. Therefore, its different aspects are worth studying. The large number of potato varieties, lack of awareness about its new cultivars among farmers to cultivate, time-consuming and inaccurate process of identifying different potato cultivars, and the significance of identifying potato cultivars and other agricultural products (in every food industry process) all necessitate new, fast, and accurate methods. The aim of this study was to use an electronic nose, along with chemometrics methods, including PCA, LDA, and ANN as fast, inexpensive, and non-destructive methods for detecting different potato cultivars. In the present study, nine sensors with the best response to VOCs were adopted. VOCs sensors were used at various VOCs concentrations (1 to 10,000 ppm) to detect different gases. The results showed that a PCA with two main components, PC1 and PC2, described 92% of the total samples’ dataset variance. In addition, the accuracy of the LDA and ANN methods were 100 and 96%, respectively.