Phenolic profile in wheat can be influenced not only by milling, extraction, cultivar and location, but also during the grain development. Metabolomics have been applied to investigate genetic diversity and to identify important characteristics of plant adaptation, technological and nutritional quality of wheat. In this study, the phenolic-profiling of 7 different wheat (Triticum aestivum) cultivars (cv.) was investigated for the first time during different stages of grain development. Free and bound phenolic compounds were extracted separately from ethanolic solution, hydrolysis, homogenization and centrifugation. Phenolic contents were determined in microplate reader by Folin-Ciocalteu and then analyzed by UPLC-MS (Xevo-G2S ESI-QTOF, Waters). Data were processed using a customized database in the Progenesis QI, considering the exact mass error (10 ppm), isotope similarity (80%), reproducibility (3/3) and parameters of 34 phenolic standards. Total phenolic contents significantly decreased towards the maturation of grain. The highest content (free and bound) was observed in milky grains cv. ORS1401, while the lowest level was found in mature grains cv. Jadeite (392.0 and 148.9 GAE mg/100 g, respectively). Globally, 206 compounds were identified, divided into 5 classes: flavonoids (77), phenolic acids (60), other polyphenols (52), lignans (11) and stilbenes (6). The same result was found by UPLC-MS, where the number of phenolic compounds progressively decreased all along grain development, milky (183), softy (177), physiological maturity (152) and mature (144). The proportion bound to free phenolic compounds increased towards mature grains, irrespective to cultivars, indicating a possible enzymatic oxidation and complexation during grain growth. Ferulic acid, isoferulic acid, 4-hydroxybenzoic acid, myricetin and caffeic acid were the most abundant compounds, found in all varieties. Noteworthy differences in phenolic profile and composition were found among cultivars and during the grain development, showing Brazilian wheat varieties contains a rich phenolic composition and may be selected according to the profile of bioactive compounds.