A protocol involving the irradiation of some 3-(2-alkenyl)estrone and 3-(2-alkenyl)-17-norestrone derivatives under a nitrogen atmosphere in organic solvents (both hexane and MeOH) followed by base-mediated intramolecular oxa-Michael cyclization reaction was investigated under steady-state conditions. The solvent effect and nature of the acyl group on the preparative photoreaction were studied and the multiplicity of the excited state was also demonstrated. The ortho-regioisomers were obtained in modest to good yields. Intramolecular based-mediate cyclization reaction of these synthons led to the formation of a set of novel substituted 4-chromanone moieties fused to estrone (and 17-norestrone) in good yields. This two-step sequential procedure involving a photochemical/intramolecular thermal cyclization strategy will be useful for the preparation of wide heterocyclic-fused-steroid compounds.