A three component reaction employing readily available starting materials: 2‐(1‐pyrrolyl)benzylamine, arylglyoxal monohydrates and electron‐deficient alkenes in the synthesis of dipyrrolobenzo[1,2‐a:2',1'‐c][1,4]diazepines ‐ previously undescribed system and indolo[2,1‐c]pyrrolo[1,2‐a][1,4]benzodiazepine derivatives have been shown. Domino reactions of pyrrolo[1,2‐a][1,4]benzodiazepines with electron‐deficient alkenes has been proposed as another approach. The applicability of the three‐component reaction for the synthesis of indolizino[8,7‐b]indole derivatives from tryptamine has been studied. The in vitro biological activity of title compounds has been tested.