The alcobaca mutation in the Penjar tomato (Solanum lycopersicum L.) variety alters the ripening process and confers a long shelf life (more than four months). Storage of Penjar tomatoes leads to a distinctive sensory profile valued by local consumers, who prefer aged tomatoes to fresh ones. To study chemical changes occurring during storage, we characterized the complete sugar-and-acid profile of 25 accessions at harvest and at 2 and 4 months after harvest. We found considerable variability in the sugar-and-acid profile within the Penjar variety, especially for fructose and glucose. Some accessions presented exceptionally high values for sugars, making them especially interesting for breeding programs. During postharvest, the concentration of glucose, fructose, and citric acid decreased, whereas the concentration of malic and glutamic acids increased. Data from this study offer novel insights into postharvest changes in tomato quality parameters and help elucidate the reasons for the appreciation of this variety by consumers.