In order to screen for a proper baking condition to improve flavor, in this experiment, we analyzed the effect of baking on the flavor of defatted tiger nut flour by electronic tongue (E-tongue), electronic nose (E-nose) and headspace solid-phase microextraction gas chromatography-mass spectrometry (HS-SPME-GC-MS). According to E-tongue and E-nose radar plots and principal component analysis (PCA), baking can effectively change the taste and odor of defatted tiger nut flour, and the odors of samples with a baking time of >8 min were significantly different from the original odor of unbaked flour. Moreover, bitterness and astringency increased with longer baking times, and sweetness decreased. HS-SPME-GC-MS detected a total of 68 volatile organic compounds (VOCs) in defatted tiger nut flour at different baking levels, and most VOCs were detected at 8 min of baking. Combined with the relative odor activity value (ROAV) and heat map analysis, the types and contents of key flavor compounds were determined to be most abundant at 8 min of baking; 3-methyl butyraldehyde (fruity and sweet), valeraldehyde (almond), hexanal (grassy and fatty), and 1-dodecanol, were the key flavor compounds. 2,5-dimethyl pyrazine, and pyrazine, 2-ethylalkyl-3,5-dimethyl- added nutty aromas, and 1-nonanal, 2-heptanone, octanoic acid, bicyclo [3.1.1]hept-3-en-2-ol,4,6,6-trimethyl-, and 2-pentylfuran added special floral and fruity aromas.