Stilbenic phytoalexins are key defence molecules implicated in the resistance of grapevine cultivars to three major fungal pathogens, Botrytis cinerea (grey mould of grape), Plamopara viticola (downy mildew) and Erysiphe necator (powdery mildew). HPLC analysis of stilbenes is an efficient method to evaluate the ability of the vine plants to inhibit the development of fungal pathogens. Resistant grapevine varieties react very rapidly to infections by producing high concentrations of the most toxic stilbenes, δ-viniferin and pterostilbene, at the sites of infection. Monitoring of such stress biomarkers is also of great interest for evaluating the efficiency of priming molecules at inducing the grapevines' natural defence responses. In addition, these compounds have various beneficial effects on human health, acting as anti-oxidants and also as potential chemopreventive agents. The diversity of stilbenes is intriguing, and new holistic analytical approaches, such as metabolomics, that are widely used for wine classification also have great potential for the comprehensive study of responses of Vitaceae to biotic and abiotic stress.