<p>The fusion of privileged heterocyclic scaffolds with biologically relevant structures represents a powerful strategy for developing novel hybrid molecules with enhanced properties. In this work, we report the preparation of flavone- and aurone-fused estrone derivatives via a sequential photo-Fries rearrangement and intramolecular annulation approach. The photo-Fries reaction of estrone 3-phenylpropiolate ester efficiently afforded <i>ortho</i>-hydroxyaryl phenylethynyl ketones, which were further cyclized under basic conditions. The selective formation of flavone (6-<i>endo-dig</i>) or aurone (5<i>-exo-dig</i>) derivatives could be tuned by varying the base strength and solvent conditions. Moreover, the aurone-fused estrone compounds exhibited visible-light-responsive photoisomerization, opening new possibilities for their application as photoswitchable steroidal systems. This photochemical strategy offers a versatile and efficient method to access functionalized steroidal derivatives with potential in chemical biology and material sciences.</p> Graphical abstract <p>A comparative investigation on the preparation of chromenones and aurones fused to estrone has been developed applying two distinct approaches, viz<i>.</i> a two sequential steps and a one-pot two-step sequence. Both methods involve the photo-Fries rearrangement and the thermal intramolecular <i>oxa</i>-Michael cyclization reactions. The last step was found to depend on the strength of the chosen base, such as KOH or K₂CO_3, to promote the 6-<i>endo</i>-dig or 5-<i>exo</i>-dig cyclization, providing the desired products in good yields.</p> <p></p>