Herein is provided an efficient and two‐step short procedure for the synthesis of novel 6H‐[1,3]dioxolobenzo[4,5‐h]pyrrolo[1,2‐a][1]benzazepin‐6‐one derivatives promoted by commercial phosphoric acid. In a parallel approach some pyrrolyl chalcones were isolated that proved to behave as intermediates for the title compounds. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)