Wine-making activity entails the production of solid and semisolid byproducts (grape stems and pomace and wine lees) that negatively impact the environment and industrial sustainability. Their features as sources of bioactive compounds support valorization procedures for functional and healthy ingredients. This work uncovers the quantitative alkyl gallates (gallic acid esters, C1−C12) profile of fresh (freeze-dried) materials and the effect of oven-drying on their stability by UHPLC-ESI-QqQ-MS/MS. The functionality was established concerning DPPH • scavenging and antihyperglycemic power. Wine lees exerted the highest high-free concentration of galloyl derivatives, ethyl gallate being the most abundant ester (3472.62 ng/g dw, on average). About the impact of the stabilization process, although as a general trend, the thermal treatment reduced the concentration, the reduction dimensions depended on the compound/matrix, remaining in valuable concentrations. Concerning radical scavenging, ze-dried stems and pomace displayed the highest capacity (24.11 and 18.46 mg TE/g dw, respectively), being correlated with propyl gallate (r 2 = 0.690), butyl gallate (r 2 = 0.686), and octyl gallate (r 2 = 0.514). These two matrices exerted α-glucosidase inhibitory activity (1.58 and 1.46 units/L) equivalent to that of acarbose (a recognized α-glucosidase inhibitor). The newly described bioactive phytochemicals in winery residues (galloyl esters) and their correlation with functional traits allow for envisioning valorization alternatives.