Wood shavings are widely employed in vinegar making to reduce aging time. Accordingly, this study aims to evaluate the effects of using shavings from different wood species (acacia, cherry, chestnut, and oak) and of toasting on the release of phenolic compounds into vinegar during the aging process. The study involved aging vinegars using previously toasted shavings and untoasted ones, at 0.5% and 1% (w/v), and collecting samples at 15 and 30 days. The phenolic compounds were analyzed by LC-DAD during the aging process. As a result, wood markers naringenin and kaempferol (cherry), robinetin and fustin (acacia), and isovanillin (oak) were identified for the first time in vinegars. The results also showed that toasting wood shavings decreases the concentration of most flavonoid wood markers (e.g., (+)-taxifolin, naringenin, and fustin) in vinegar, but that it is essential for the highest releases of aldehyde compounds (syringaldehyde, protocatechualdehyde, and vanillin). Remarkably, 15 days was sufficient to obtain the highest increases of most polyphenol compounds in the vinegar. Statistical analysis (linear discriminant analysis) proved that the phenolic compounds identified in vinegars are useful for discriminating vinegars regarding the wood species of the shavings used to accelerate aging.