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 were also obtained. [28]Hexaphyrin 4 was quantitatively oxidized to [26]hexaphyrin 14 with MnO(2). These expanded porphyrins have been characterized by mass spectrometry, (1)H and (19)F NMR spectroscopy, and UV/Vis spectroscopy. The single-crystal structures have been determined for 3, 4, 6, 7, and 14. The N-fused [24]pentaphyrin 3 displays a distorted structure containing a tricyclic fused moiety that is similar to those of meso-aryl-substituted counterparts, whereas 8 and 9 are indicated to take roughly planar conformations with an inverted pyrrole opposite to the sp(3)-hybridized meso-carbon atom. Both [28]- and [26]hexaphyrins 4 and 14 have figure-of-eight structures. Solid-state structures of the decaphyrin 6 and dodecaphyrin 7 are remarkable, exhibiting a crescent conformation and an intramolecular two-pitch helical conformation, respectively.