β-Carbolines (βCs) are naturally occurring bioactive alkaloids, whereas α-dicarbonyl compounds are reactive substances generated in foods and in vivo. In this work, l-tryptophan reacted with α-dicarbonyl compounds affording new β-carbolines. Glyoxal afforded 1-hydroxymethyl-β-carboline (HME-βC) and its 3-carboxylic acid, and methylglyoxal afforded 1-(1-hydroxyethyl)-β-carboline (HET-βC) and its 3-carboxylic acid. 3-Deoxyglucosone afforded 1-(1,3,4,5-tetrahydroxypent-1-yl)-β-carboline isomers (1a/b), 1-(1,4,5-trihydroxypent-1-yl)-β-carboline (2), and 1-(1,5-dihydroxypent-3-en-1-yl)-β-carboline (3). The formation of these βCs increased under acidic conditions and with increasing temperature. A mechanism is proposed explaining the conversion of a carbonyl into a hydroxy group based on tautomerism and cyclization to the dihydro-βC-3-COOH intermediates, which were isolated and gave the βCs. These α-dicarbonyl-derived βCs occurred in model reactions of l-tryptophan with fructose or glucose incubated under heating and can be considered as advanced glycation end products (AGEs). They were also present in foods and formed during heating processes. HET-βC appeared in processed foods, reaching up to 309 ng/g, with the highest amount found in dried tomato, fried onion, toasted bread, and Manuka honey. HME-βC was only detected in some foods with lower amounts than HET-βC. HET-βC appeared in foods as a racemic mixture of enantiomers suggesting the same mechanism of formation as the synthetized product. α-Dicarbonyl-derived βCs (HET-βC, HME-βC, and 1a/b-3) occur in foods and food processing and, therefore, they are ingested during diet. © 2022 American Chemical Society.