A comprehensive study based on the profiling and quantification of the volatile composition and the application of descriptive sensory analysis of 25 commercial monovarietal white wines (var. Xarel.lo) from different vintages and from representative wine cellars along the Penedés region (Catalonia, Spain) was performed in order to characterize representative wines that are being commercialized under the O.D. Penedés. In addition, relationships between the instrumental (volatile) and sensory variables were found through the application of partial least squares regression. The results showed great differences between younger wines and wines that underwent the crianza (or ageing) process. The first group of wines was characterized by a marked fruity and floral odour and fresh taste, while the second group was characterized by more complex sensory attributes such as toasted, spicy and compote odour attributes. These differences in sensory characteristics were related to a higher content of higher alcohol acetates and ethyl and methyl esters of fatty acids in wines included in the first group, while the second group was characterized by a lower concentration of esters, but higher concentration of compounds related to wine ageing, such as furfural, 5-methylfurfural and vitispiranes.