In this work, we describe the development of the rearrangement for 7-aryl-substituted oxazolo [5,4-b]pyridines treated with aluminum chloride into synthetically hard-to-reach benzo [c][1,7]naphthyridinones. The discovered rearrangement is applied to a variety of electron-rich (hetero)arene substrates. It offers the advantages of mild conditions (90 °C temperature), fast reaction rates (<4 h), compatibility with air moisture, and the use of inexpensive commercial reagents. The proposed reaction mechanism and key elementary reaction acts were studied in detail using quantum chemical calculations. The photophysical properties of the synthesized compounds were studied by steady-state UV−vis spectroscopy.