Polysaccharides are the main group of macromolecules in wines. Climate change is a major problem for viticulturists as it leads to the production of unbalanced grapes. This is attributed to a mismatch between the technological maturity and phenolic maturity of grapes, which can negatively impact the production of high quality wines. To mitigate this effect, biostimulants can be applied to grapevines. For the first time in the literature, this work studied the foliar application of methyl jasmonate plus urea (MeJ + Ur) on the vineyard and its effect on the monosaccharide and polysaccharide composition of Tempranillo grapes and wines over two consecutive seasons. To achieve this, the extraction and precipitation of polysaccharides was conducted, and the identification and quantitation of monosaccharides was performed via GC–MS. The effect of MeJ + Ur foliar treatment in both the grapes and wines was season-dependent. The MeJ + Ur treatment had a slight impact on the monosaccharide composition of the grapes and also demonstrated a small effect on the wines. Multifactor and discriminant analysis revealed that the season had a greater influence on the monosaccharide and polysaccharide composition of grapes and wines compared to the influence of MeJ + Ur treatment. Interestingly, the MeJ + Ur-treated wines exhibited a higher sensory evaluation than the control wines in the second vintage. To gain further insights into the effect of MeJ + Ur foliar application on the monosaccharide and polysaccharide composition of grapes and wines, further investigations should be conducted.