Abstract A series of meso-trifluoromethyl-substituted expanded porphyrins, including N- fused [24] pentaphyrin 3,[28] hexaphyrin 4,[32] heptaphyrin 5,[46] decaphyrin 6, and [56] dodecaphyrin 7, were synthesized by means of an acid-catalyzed one-pot condensation reaction of 2-(2, 2, 2-trifluoro-1-hydroxyethyl) pyrrole (1) as the first examples bearing meso- alkyl substituents. Besides these products, porphyrin 2 and two calix [5] phyrins 8 and 9 ...