The effect of heat processing on the flavor characteristics of highland barley flour (HBF) in storage was revealed by analyzing differences in volatile compounds associated with flavor deterioration in HBF using GC-MS identification and relative odor activity values (ROAVs). Hydrocarbons were the most abundant in untreated and extrusion puffed HBFs, while heterocycles were found to be the most abundant in explosion puffed, baked, and fried HBFs. The major contributors to the deterioration of flavor in different HBFs were hexanal, hexanoic acid, 2-pentylfuran, 1-pentanol, pentanal, 1-octen-3-ol, octanal, 2-butyl-2-octanal, and (E,E)-2,4-decadienal. Amino acid and fatty acid metabolism was ascribed to the main formation pathways of these compounds. Baking slowed down the flavor deterioration in HBF, while extrusion puffing accelerated the flavor deterioration in HBF. The screened key compounds could predict the quality of HBF. This study provides a theoretical basis for the regulation of the flavor quality of barley and its products.