The evolution of almost 40 oak-related volatile compounds and the sensorial characteristics of red wines from four Spanish denominations of origin (DOs) (Bierzo, Toro, Ribera de Duero, and Rioja) during aging in barrels made of Rebollo oak wood, Quercus pyrenaica, were studied and compared to the same wines aged in American and French oak barrels. Each oak wood added unique and special characteristics to the wine, and in addition, each wine showed a different ability to extract the compounds, which result in these characteristics from the oak wood. In general, wines aged in Q. pyrenaica wood were characterized by high levels of eugenol, guaiacol, and other volatile phenols. In regards to compounds like cis-whiskylactone or maltol, the behavior of this wood is very similar to that of American oaks. When considering phenolic aldehydes and ketones, the levels of these compounds are intermediate between those of French and American woods and depend greatly on the type of wine. The type of oak, on the other hand, does not affect the chromatic characteristics of the wines. In sensory analysis, the biggest differences are found in the olfactory phase. Among the four DOs studied, wine aged in Q. pyrenaica presented the highest notes of wood, with more aromas of roasting, toasting, milky coffee, spices, or wine-wood interactions. The wines aged in barrels made of Q. pyrenaica wood were highly regarded, and preference was shown for them over those same wines when they had been aged in barrels of American or French oak.