Astringency is an important red wine quality attribute, which can be measured both chemically and sensorially. The use of tannin activity shows potential as a valuable chemical measurement in understanding red wine mouthfeel properties such as astringency and bitterness, which is also affected by tannin structural factors, in addition to matrix effects. Tannin activity is defined as the enthalpy of interaction between tannins and a hydrophobic surface. Studies involving tannin activity have been performed since the early 2010’s, but chemosensory studies used to evaluate how structure-activity relationships change across multiple, consecutive vintages are limited. The aim of this study is to investigate how tannin activity may be linked to red wine mouthfeel, and how all these variables may change according to wine age.