The quality of wines has often been associated with their geographical area of production, as well as the grape variety used in their elaboration. Many research studies have been carried out to characterize and differentiate between red wines labeled with Protected Designation of Origin (PDO) from different geographical areas, but very few have been carried out on white and rosé wines. The objective of this work was to characterize white and rosé PDO wines from different geographical areas of Spain very close to each other elaborated with different grape varieties and select the variables that most contribute to their differentiation. Analysis of variance (ANOVA) and principal component analysis (PCA) were used as statistical methods. The ethanol content was the nonvolatile variable that most contributed to differentiating between some of the white and rosé wines according to their PDO. The white wines from RD (Ribera del Duero) and BI (Bierzo) were characterized by a high terpenic content (floral notes) while the wines from RU (Rueda), TO (Toro) and CI (Cigales)by a high content of ethyl esters and alcohol acetates (fruity aromas). The rosé wines elaborated with the Mencía grape variety from BI were characterized by their highest polysaccharidic content, which could have a positive sensory effect on the mouthfeel. The rosé wines from CI were characterized by their volatile profile complexity, having the highest content of volatile compounds from the oak wood, terpenes and C6 alcohols which provide pleasant woody, floral and herbaceous aromas. On the contrary, the RD wines were richest in alcohol acetates responsible for fruity aromas.