This study evaluated the relationship among palatability attributes, volatile compounds, and fatty acid (FA) profiles in meat from barley, corn, and blended (50:50, barley and corn) grain-fed steers. Multiple correspondence analysis with three dimensions (Dim) explained 62.2% of the total variability among samples. The Dim 1 and 2 (53.3%) separated pure from blended grain-fed beef samples. Blended grain beef was linked to a number of volatiles including (E,E)-2,4-decadienal, hexanal, 1-octen-3-ol, and 2,3-octanedione. In addition, blended grain-fed beef was linked to fat-like and rancid flavors, stale-cardboard, metallic, cruciferous, and fat-like aroma descriptors, and negative categories for flavor intensity (FI), off-flavor, and tenderness. A possible combination of linoleic and linolenic acids in the blended diet, lower rumen pH, and incomplete biohydrogenation of blended grain-fed polyunsaturates could have increased (p ≤ 0.05) long-chain n-6 fatty acids (LCFA) in blended grain-fed beef, leading to more accumulation of FA oxidation products in the blended than in barley and corn grain-fed meat samples. The Dim 3 (8.9%) allowed corn separation from barley grain beef. Barley grain-fed beef was mainly linked to alkanes and beef positive FI, whereas corn grain-fed beef was associated with pyrazines, in addition to aldehydes related to n-6 LCFA oxidation.