The sulfa-Michael/aldol cascade reaction of 1,4-dithiane-2,5-diol to 2-NO2-porphyrin has been developed, and this method provides a new facile approach to tetrahydrothiophene-fused porphyrin. Thermal methodologies drive dehydration and aromatization of tetrahydrothiophene-fused porphyrin to form thiophene-fused porphyrin in high yield. The peripheric fused-thiophene did not change the coordination properties of the porphyrin to Zn(II) and Ni(II).