Buckwheat is a rich source of phenolic compounds that have shown to possess beneficial effect to reduce some diseases due to their antioxidant power. Phenolic compounds are present in the free and in the bound form to the cell wall that are concentrated mainly in the outer layer (hull and bran). Hull is removed before the milling of buckwheat to obtain flours. In order to evaluate the phenolic composition in dehulled buckwheat milling fractions, it was carried out a determination of free and bound phenolic compounds in dehulled whole buckwheat flour, light flour, bran flour, and middling flour by high-performance liquid chromatography-mass spectrometry (HPLC-MS). The most abundant free phenolic compounds were rutin and epiafzelchin-epicatechin-O-dimethylgallate, whereas the most abundant bound phenolic compounds were catechin and epicatechin in all buckwheat flours. Besides, the highest content of free phenolic compounds was obtained in bran flour (1249.49 mg/kg d.w.), whereas the greatest bound phenolic content was in middling (704.47 mg/kg d.w.) and bran flours (689.81 mg/kg d.w.). Thus, middling and bran flours are naturally enriched flours in phenolic compounds that could be used to develop functional foods.