In this study, we investigated the combined effects of MoS2 QDs’ catalytic properties and the colorimetric responses of organic reagents to create a sniffing device based on the sensor array concept of the mammalian olfactory system. The aim was to differentiate the volatile organic compounds (VOCs) present in cigarette smoke. The designed optical nose device was utilized for the classification of various cigarette VOCs. Unsupervised Principal Component Analysis (PCA) and supervised Linear Discriminant Analysis (LDA) methods were employed for data analysis. The LDA analysis showed promising results, with 100% accuracy in both training and cross-validation. To validate the sensor’s performance, we assessed its ability to discriminate between five cigarette brands, achieving 100% accuracy in the training set and 82% in the cross-validation set. Additionally, we focused on studying four popular Iranian cigarette brands (Bahman Kootah, Omega, Montana Gold, and Williams), including fraudulent samples. Impressively, the developed sensor array achieved a perfect 100% accuracy in distinguishing these brands and detecting fraud. We further analyzed a total of 126 cigarette samples, including both original and fraudulent ones, using LDA with a matrix size of (126 × 27). The resulting LDA model demonstrated an accuracy of 98%. Our proposed analytical procedure is characterized by its efficiency, affordability, user-friendliness, and reliability. The selectivity exhibited by the developed sensor array positions it as a valuable tool for differentiating between original and counterfeit cigarettes, thus aiding in border control efforts worldwide.