Common wheat (Triticum aestivum) is one of the most consumed staple foods used for bakery products. Outer layers of grain present a great diversity of bioactive compounds, especially phenolic compounds (PC). Free and bound PC were extracted from eight genotypes of whole wheat flours (WWF) presenting different technological classifications. These extracts were comprehensively characterized through untargeted metabolomics applying ultra-high-performance liquid chromatography-mass spectrometry (UHPLC-MSE) and spectrophotometric analyses. Chemical composition and colorimetry were also determined by classical analyses. Thirty-eight PC were tentatively identified by UHPLC-MSE belonging to three classes (phenolic acids, flavonoids, and other polyphenols), some of them identified in all WWF samples. Bound hydroxycinnamic acids were the main PC found in WWF, especially the trans-ferulic acid and its isomer. No difference was found in starch and protein contents, whereas low-quality flours showed a higher ash content than the superior and medium-quality flours. Total phenolic content (TPC) ranged between 124.5 and 171.4 mg GAE/100 g WWF, which bound PC were responsible for 60% of TPC. Omics data and multivariate statistical analyses were successfully applied to discern the phenolic profile of WWF from different genotypes and technological qualities.