Toxic α-dicarbonyl compounds, glyoxal, 2-methylglyoxal, and diacetyl, released from the headspace from butter, margarine, safflower oil, beef fat, and cheese heated at 100 and 200 °C were analyzed by gas chromatography as quinoxaline derivatives. Total amounts of α-dicarbonyl compounds ranged from 40.5 ng/g (butter) to 331.2 ng/g (beef fat) at 100 °C and from 302.4 ng/g (safflower oil) to 4521.5 ng/g (margarine) at 200 °C. The total amount of α-dicarbonyl compounds increased approximately 55- and 15-fold in the headspace of heated butter and margarine, respectively, when the temperature was increased from 100 to 200 °C. However, only slight differences associated with temperature variation were observed in the cases of safflower oil and beef fat (1.3- and 1.1-fold, respectively). Diacetyl was found in the highest amounts among all samples, ranging from 13.9 ± 0.3 ng/g (butter) to 2835.7 ng/g (cheese) at 100 °C and from 112.5 ± 102 ng/g (safflower oil) to 2274.5 ± 442.6 ng/g (margarine) at 200 °C, followed by methylglyoxal, ranging from 13.0 ± 0.5 to 112.7 ± 10.1 ng/g (cheese) at 100 °C and from 34.7 ± 5.0 ng/g (safflower oil) to 1790 ± 372.3 ng/g (margarine) at 200 °C. Much less glyoxal formed, in amounts ranging from 13.6 ± 0.7 ng/g (butter) to 53.4 ± 11.2 ng/g (beef fat) at both temperatures. The amounts of α-dicarbonyl compounds released into the vapor phase from lipid commodities during heating were satisfactorily analyzed.