Foods of plant origin contain a large number of phytochemicals that may positively affect health. Phytochemicals are largely excreted in urine as metabolites that are formed in host tissues or by the microbiota and constitute a great proportion of the urinary metabolome. The latter can be characterized by a metabolomics approach. In this work, we compared the metabolism of lignins to that of the structurally related ferulic acid (FA) and sinapic acid (SA). Five groups of rats (n = 5) were fed for 2 d a purified diet alone [control (C)] or supplemented with lignin-enriched wheat bran (3% of the diet, wt:wt), poplar wood lignins (0.42%), FA (0.42%), or SA (0.42%). The metabolomes of urine samples collected after 1 and 2 d of supplementation were analyzed by high-resolution MS (liquid chromatography/quadrupole time-of-flight). Comparing metabolic fingerprints by gathering semiquantitative information on several hundreds of metabolites and using multivariate statistical analysis (partial least squares for discriminant analysis) showed the similarity between both lignin-supplemented and C groups and confirmed that lignins are largely inert and not absorbed in the body. One the other hand, metabolic fingerprints of the 2 phenolic acid-supplemented groups were clearly distinct from the C group. Differences between the groups were mainly from nonmetabolized FA and SA and metabolites excreted in urine. Thirteen of them were identified as sulfate esters and glucuronide and glycine conjugates of the same phenolic acids, and of dihydrosinapic, vanillic, and benzoic acids. This study shows that metabolomics allows the identification of new metabolites of phytochemicals and can be used to distinguish individuals fed different phytochemical-containing foods.