This study investigated the dietary supplementation of starches with different carbohydrate sources on the proximate composition, meat quality, flavor substances, and volatile flavor substances in the meat of Chinese Xiangxi yellow cattle. A total of 21 Chinese Xiangxi yellow steers (20 ± 0.5 months, 310 kg ± 5.85 kg) were randomly divided into three groups (control, corn, and barley groups), with seven steers per group. The control steers received a conventional diet (coarse forage type: whole silage corn at the end of the dough stage as the main source), the corn group received a diet with corn as the main carbohydrate source, and the barley group received a diet with barley as the main carbohydrate source. The experiment lasted for 300 d. and the means of the final weights in the control, corn, and barley groups were 290 kg, 359 kg, and 345 kg. The diets were isonitrogenous. The corn and barley groups reduced the moisture (p = 0.04) and improved the intramuscular fat content of the meat (p = 0.002). They also improved meat color (a*) (p = 0.01) and reduced cooking loss (p = 0.08), shear force (p = 0.002), and water loss (p = 0.001). There was no significant difference in the 5'-nucleotide content (p > 0.05), the equivalent umami concentration (EUC) (p = 0.88), and taste activity value (TAV) (p > 0.05) among the three groups. The 5'-IMP (umami) content was the highest in the 5'-nucleotide and its TAV > 1. The corn and barley groups improved the content of tasty amino acids (tAA, p < 0.001). The corn group had a higher content of sweet amino acids (SAA, p < 0.001) and total amino acids (TAA, p = 0.003). Corn and barley improved the levels of MUFA (p < 0.001), PUFA (p = 0.002), n-3 PUFA (p = 0.005), and n-6 PUFA (p = 0.020). The levels of alcohols, hydrocarbons, and aldehydes in the corn group were higher than in the barley and control groups (p < 0.001). The esters content in the corn group was higher than in the barley and control groups (p = 0.050). In conclusion, feeding corn or barley as a carbohydrate source can improve the nutrient content and taste. Feeding corn as a carbohydrate source can improve the content of free amino acids (Cys, Glu, Gly, Thr, Leu, Trp, Gln, Asn, and Asp), fatty acids (saturated fatty acid, monounsaturated fatty acid, polyunsaturated fatty acid, n-3PUFA, n-6PUFA, and total fatty acid), and volatile flavor substances (alcohols, aldehydes, acids, and hydrocarbons) to improve the flavor and meat quality.