The analytical and sensory analysis of wines aged in barrels of French and American oak with three different levels of toasting was performed to determine the relationship between the volatile substances released by oak wood and sensory appreciation by a trained panel. For that purpose, a discolored white wine of Macabeo and a red wine of Cabernet Sauvignon from 2012 vintage were aged for 12 months in new barrels. Similar wines from the following vintage were aged in the same barrels for knowing how the use of the barrels affects their capacity to release volatile substances and its organoleptic impact. A significant correlation was found between the appreciation of coconut and smoked/toasted notes by the panel and the theoretical sensory impact of β-methyl-γ-octalactone and volatile phenols, respectively, in two different wines aged in new oak barrels. Vanillin correlated significantly in only one of the wines tasted. The panelists generally preferred wines aged in medium-toasted new barrels for both oak species. In a triangle test, tasters could distinguish between wines aged in new American and French oak barrels when the toasting level was light or medium but not when it was heavy. They were also able to distinguish between wines aged in new and 1-year-used barrels. It can be concluded that the botanical origin of the oak, the toasting level of the staves and the number of times that the barrels have been used previously have a real impact on the volatile composition of the wine and in its sensory impact.