A series of pyrrolo[3,2‐f]quinoxaline derivatives have been obtained by a three‐component domino reaction of quinoxalin‐6‐amine, arylglyoxal monohydrates, and cyclic 1,3‐dicarbonyl compounds in ethanol medium at 80°C catalyzed by acetic acid. The notable features of this synthesis are excellent regioselectivity, operational simplicity, relatively mild reaction conditions, and good yields.