Polyphenols are a diverse group of compounds possessing various health-promoting properties that are of utmost importance for many wine sensory attributes. Apart from genetic and environmental parameters, the implementation of specific oenological practices as well as the subsequent storage conditions deeply affect the content and nature of the polyphenols present in wine. However, polyphenols are effectively employed in authenticity studies. Provision of authentic wines to the market has always been a prerequisite meaning that the declarations on the wine label should mirror the composition and provenance of this intriguing product. Nonetheless, multiple cases of intentional or unintentional wine mislabeling have been recorded alarming wine consumers who demand for strict controls safeguarding wine authenticity. The emergence of novel platforms employing instrumentation of exceptional selectivity and sensitivity along with the use of advanced chemometrics such as NMR (nuclear magnetic resonance)- and MS (mass spectrometry)-based metabolomics is considered as a powerful asset towards wine authentication.