In the last decade, “expressions” of grape marc spirits aged in wooden barrels of characteristic amber color and complex sensory attributes have been introduced. Yet studies on constituents migrating from the barrel to the beverage are scarce, and their metabolic profile remains unexplored. Furthermore, the literature on the assessment of their antioxidant activity is limited. NMR metabolomics and spectrophotometry have been implemented in 38 samples to elucidate the impact of the aging procedure on the metabolites’ composition and establish whether these beverages exhibit antioxidant activity. Provenance was related to fusel alcohols, esters, acetaldehyde, methanol, saccharides, and 2-phenylethanol, while ethyl acetate and ethyl lactate contributed to discriminating samples of the same winery. Identified metabolites such as vanillin, syringaldehyde, and sinapaldehyde were related to the aging procedure. The maturation in the barrel was also associated with an increase in xylose, glucose, fructose, and arabinose. The antioxidant potential of the aged Greek grape marc spirits resulting from their maturation in oak barrels was highlighted. The metabolic profiling and antioxidant potential of aged Greek grape marc spirits were assessed for the first time. Finally, the enrichment of the aromatic region was noted with the presence of metabolites with a furanic and phenolic ring derived, respectively, from the polysaccharides’ degradation or the thermal decomposition of lignin.