Understanding the molecular basis for the astringent response of red wine remains an active area of research. The first component of this review examines the evidence for the existence of molecular assembly processes, particularly involving proanthocyanidins, proteins and polysaccharides. The need for competitive studies involving other wine components on the aggregation processes is identified. Secondly, we examine the impact of molecular assembly on the methodology used to assess astringency, arguing that gustation experiments should be designed around wine in its natural state. Finally, the possibility of finding commonalities between sensory descriptors for astringency and analytical measurements on the wine in its natural state is outlined.