Grains, leaves, sheaths, glumes and stalks of sorghum varieties were analyzed for total phenols, condensed tannins, flavan-4-ols, anthocyanins and in vitro antioxidant activity. Black sorghum bran was used to evaluate the effectiveness of organic acids and enzymes on extractability of phenols. Flavonoid profiles of grains and non-grain tissues were determined and characterized using HPLC-PDA and HPLC-ESI-MSn. The presence of a pigmented testa and spreader genes (B1B2S) is a predictor for polymeric flavonoids (tannins) but not for simple phenols such as flavan-4-ols, 3-deoxyanthocyanins, flavones and flavanones. Simple flavonoids increased antioxidant capacity of sorghum, and were present in all sorghum except for the white pericarp sorghums that did not have flavanones. The "red turning into black" gene increased phenols in Type I sorghum. The leaves, sheath and glumes of sorghum had higher levels of phenols (78-600 times more), with in vitro antioxidant properties than commonly seen in grains. Pigmentation of plant components increased levels of 3- deoxyanthocyanins but not flavones nor flavanones. The leaves of biomass sorghum, Collier variety, had 3.4 times more 3-deoxyanthocyanins than the leaves of Tx430 Black x Sumac which had the highest levels (1810 ?g/g) of 3- deoxyanthocyanins among the leaves. The use of 1% HCl/ethanol provides a possible food grade substitute solvent for 1%HCl/methanol in the extraction of phenolic compounds from sorghum. All enzymes evaluated broke down bran particles forming a gel-like material which had increased phenols and antioxidant activities but not 3- deoxyanthocyanins as revealed by HPLC analysis. Microscopy examination showed the gel matrix rich in fiber and can possibly be used for nutraceutical applications. Careful understanding of enzyme activities is necessary for effective extraction of 3-deoxyanthocyanins from sorghum. Sorghum leaves, sheaths and glumes are excellent sources of bioactive compounds, up to 600 times more than the grains of some varieties. Sorghum with the "red turning to black genes" is a potential source of 3- deoxyanthocyanins and flavan-4-ols. With the trend towards sorghum as biomass for ethanol production, plant breeders must select special traits aimed at developing enhanced desired functionality such as antioxidant potential and other healthy attributes with application in food, pharmaceutical/nutraceutical and cosmetic industries.