The present research shows a robust isotopic ratio characterization of Carbon-13 (δ¹³C_VPDB) in congeneric compounds such as methanol, n-propanol, isoamyl alcohol, ethyl lactate, ethyl acetate, ethanol, and acetaldehyde in representative samples (n = 69) of Tequila 100% agave silver class (TSC), employing gas chromatography/combustion/isotope-ratio mass spectrometry (GC/C/IRMS). From the information obtained, the construction of a radial plot attributable to the isotopic fingerprint of TSC was achieved. With this information, a diagnostic test was designed to determine the authenticity of TSC, comparing alcoholic beverages from other agave species as non-authentic samples. The sensitivity of the test was 94.2%; the specificity was 83.3%. Additionally, non-authentic samples were analyzed that meet all the criteria established in the regulations. The results obtained show that the GC/C/IRMS analytical technique and designed diagnostic test are useful as auxiliary parameters to determine the authenticity of the beverage, thus managing to determine the adulteration or falsification of the product.