Wine polyphenols (PPhs) and volatile organic compounds (VOCs) are responsible for two of the main sensory characteristics in defining the complexity and quality of red wines: astringency and aroma. Wine VOCs’ volatility and solubility are strongly influenced by the matrix composition, including the interactions with PPhs. To date, these interactions have not been deeply studied, although the topic is of great interest in oenology. This article reviews the available knowledge on the main physicochemical and sensory effects of polyphenols on the release and perception of wine aromas in orthonasal and retronasal conditions. It describes the molecular insights and the phenomena that can modify VOCs behavior, according to the different chemical classes. It introduces the possible impact of saliva on aroma release and perception through the modulation of polyphenols–aroma compounds interactions. Limitations and possible gaps to overcome are presented together with updated approaches used to investigate those interactions and their effects, as well as future perspectives on the subject.