The photo-induced rearrangement of 2'-arylisoflavones (aryl = phenyl, furyl, 3-pyridyl, 1-naphenyl, and 2-naphenyl) for the synthesis of (2-hydroxyphenyl)(fused phenyl)methanones in EtOH under an Ar atmosphere at room temperature has been developed. The described method proceeded smoothly without requiring any transition metal catalyst, oxidant, or additives. Moreover, using ethanol as the solvent is not only cost efficient but also environmentally friendly. Further treatment of methanone analogues with AlCl3 yielded highly conjugated polycyclic aromatic hydrocarbon (PAH) derivatives.