Grape antioxidant dietary fiber (GADF) combines the putative health benefits of fiber and polyphenols. Polyphenolic metabolites may play a key role in the overall biological effects of this supplement. We identified phenolic GADF metabolites in rat urine at different times after oral administration, using HPLC-ESI-MS/MS techniques. The phenolic metabolic outcome of GADF is essentially an array of mono- and polyconjugated epicatechins and free or conjugated smaller phenolic acids, some of them never reported before. We have detected 18 mono-, di-, and triconjugates of epicatechin with glucuronide, methyl and sulfate moieties and small phenolic acids both free and conjugated. The results suggest that the procyanidin oligomers are both depolymerized in the digestive tract into epicatechin conjugates and degraded by the colonic microbiota into phenolic acids and their conjugates. For several hours after ingestion of GADF, a great variety of phenolic species, including some with an intact catechol group, are in contact with the digestive tract tissues before, during and after metabolization, and many of them are systemically bioavailable before being excreted.