SDS–PAGE electrophoresis and densitometry analysis were carried out to evaluate the reactivity of Aglianico red grape skin and seed polyphenols with human salivary proteins in order to find a method able to assess their astringency. Analysis of the supernatant obtained after a tannin/human salivary protein binding assay and sensorial analysis showed that four proteins, lactoferrin, PRPbg1, PRPbg2 and α-amylase, were the proteins best able to distinguish tannin solutions characterised by different levels of astringency. A correlation between densitometric data and tannin concentration was plotted in order to give an indirect measure of astringency. The two sources of Aglianico grape polyphenols differed from each other in astringency power; the seed extract solution was about two-fold more tannic than the skin one. The difference in astringency was also perceived by sensorial analysis. The results from this study show that SDS–PAGE electrophoresis of human salivary proteins after the binding reaction with grape polyphenol extracts, coupled with densitometric analysis and the use of a calibration curve, looks extremely promising as a new approach to evaluate polyphenol astringency.