An electronic nose (E-nose), comprising eight metal oxide semiconductor (MOS) gas sensors, was used in situ for real-time classification of black tea according to its quality level. Principal component analysis (PCA) coupled with signal preprocessing techniques (i.e., time set value preprocessing, F1; area under curve preprocessing, F2; and maximum value preprocessing, F3), allowed grouping the samples from seven brands according to the quality level. The E-nose performance was further checked using multivariate supervised statistical methods, namely, the linear and quadratic discriminant analysis, support vector machine together with linear or radial kernels (SVM-linear and SVM-radial, respectively). For this purpose, the experimental dataset was split into two subsets, one used for model training and internal validation using a repeated K-fold cross-validation procedure (containing the samples collected during the first three days of tea production); and the other, for external validation purpose (i.e., test dataset, containing the samples collected during the 4th and 5th production days). The results pointed out that the E-nose-SVM-linear model together with the F3 signal preprocessing method was the most accurate, allowing 100% of correct predictive classifications (external-validation data subset) of the samples according to their quality levels. So, the E-nose-chemometric approach could be foreseen has a practical and feasible classification tool for assessing the black tea quality level, even when applied in-situ, at the harsh industrial environment, requiring a minimum and simple sample preparation. The proposed approach is a cost-effective and fast, green procedure that could be implemented in the near future by the tea industry. Author Contributions: Conceptualization, K.T. and A.M.P.; Data curation, I.F., D.L., and N.N.; Formal analysis, S.N.H., K.T., A.C.A.V. and A.M.P.; Funding acquisition, K.T.; Investigation, I.F.; Methodology, K.T., T.J., A.C.A.V.; Project administration, T.J.; Resources, Y.Y. and N.N.; Software, S.N.H., A.C.A.V. and A.M.P.; Supervision, K.T. and N.N.; Validation, K.T., T.J., Y.Y.; Visualization, D.L. and A.M.P.; Writing-original draft, S.N.H., D.L.; Writing-review & editing, K.T., A.C.A.V., A.M.P.