The application of biostimulants appears to be an environmentally friendly, innovative, and sustainable agronomical tool to mitigate the negative effects induced by adverse climatology in traditional grape-growing regions such as La Rioja (Spain). However, their mechanism of action in grapevines is still unclear. We evaluated how commercial substances (two from Ascophyllum nodosum extraction and one amino acids-based biostimulant) and the non-proteinogenic amino acid β-aminobutyric acid (BABA) affect the quality and quantity of musts and grapes in Vitis vinifera L. cv. Tempranillo from a semi-arid region of La Rioja during two seasons. We hypothesized an enhancement in organic metabolites in berries and leaves in response to these treatments, changing the organoleptic characteristics of the final products. The treatments altered the primary metabolites such as carbohydrates, organic acids (AcOrg), and free amino acids, first in the leaves as the effect of the foliar application and second in grapes and musts. As the main result, the biostimulant efficiency depended on the climatology and vineyard location to improve the final yield. Whereas biostimulant application enhanced the yield in 2018 (less dry year), it did not help production in 2019 (dry year). BABA was the most efficient biostimulant, enhancing plant production. Regarding yield quality, the biostimulant application improved the musts mainly by enhancing the fumaric acid content and by reducing carbohydrates, except in BABA-treated plants, where they were accumulated. These results corroborate biostimulants as an exciting approach in wine production, especially for improving wine quality.