•Terpene profiles could discriminate five wine grape varieties at five E-L stages.•Shiraz and Cabernet Sauvignon had consistent evolution patterns for total norisoprenoids and sesquiterpenes.•(E)-β-Damascenone concentration increased along with the berry maturation in all varieties.•Sesquiterpenes showed a ‘U’ shape evolution pattern for most varieties in both vintages. Terpenes and their derivatives, terpenoids, are important biomarkers of grape quality as they contribute to flavor and aroma of grape and wine. The evolution of terpene and terpenoids throughout grapevine phenological development cycles is not well understood. The current study investigated the volatile profiles of free terpene and terpenoid of five widely grown Vitis vinifera L. cultivars (Shiraz, Cabernet Sauvignon, Riesling, Chardonnay and Pinot Gris), at different phenological stages from fruit-set to harvest. 17 Monoterpenoids, 3 norisoprenoid and 13 sesquiterpenoids were identified and quantified. Discriminant analysis revealed that for each grape cultivar, free terpene profiles at different E-L stages were distinctive. When integrating total sugar, total terpenes and the cumulated heat index, it could be found that flavor ripening was more consistent with sugar ripening in the warmer vintage 2016. Comparing the two red wine varieties, the overall development patterns of total monoterpenes, norisoprenoids and sesquiterpenes were similar.