Extrusion temperature (120, 135, and 150 °C) and quantity of added sodium hydroxide (0, 3, and 6 g/kg feedstock) were used as variables to study flavor generation in extrusion cooking of wheat flour. In total, 127 volatile components were identified in the extrudates, of which 51 contained sulfur. The levels of pyrroles, thiophenes, thiophenones, thiapyrans, and thiazolines increased at higher extrusion temperatures, whereas furans and aldehydes decreased. The addition of sodium hydroxide also affected the formation of volatile compounds. However, thiophenes, thiophenones, polythiacycloalkanes, thiazoles, thiazolines, pyrroles, and some pyrazines tended to increase with the more alkaline extrusion conditions. Some compounds from lipid−Maillard interactions were identified in the extrudates. Analysis of the volatile components by gas chromatography−olfactometry showed sulfur- and nitrogen-sulfur-containing heterocycles as possible contributors to the sulfury and rubbery odors observed in extrudates produced at the higher temperature and more alkaline conditions.