Trifluoroacetic acid-catalyzed condensation of pyrrole with electron-deficient and sterically hindered 3,5-bis(trifluoromethyl)benzaldehyde results in the unexpected production of a series of meso-3,5-bis(trifluoromethyl)phenyl-substituted expanded porphyrins including [22]sapphyrin 2, N-fused [22]pentaphyrin 3, [26]hexaphyrin 4, and intact [32]heptaphyrin 5 together with the conventional 5,10,15,20-tetrakis(3,5-bis(trifluoromethyl)phenyl)porphyrin 1. These expanded porphyrins are characterized by mass spectrometry, (1)H NMR spectroscopy, UV/Vis/NIR absorption spectroscopy, and fluorescence spectroscopy. The optical and electrochemical measurements reveal a decrease in the HOMO-LUMO gap with increasing size of the conjugated macrocycles, and in accordance with the trend, the deactivation of the excited singlet state to the ground state is enhanced.